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PARRY’S

CYCLOPEDIA OF PERFUMERY

i FOURKEAU'S PREPARATION OF
, ORGANIC ]MEDIGAI\IENTS. Translated by
i W. A. SiLViiSTHR, M.Sc. 22 Illustrations.

! THE BOOK OF RECEIPTS. ByE.W. Lucas,

, C.D.IL, F.I.C., and H. B. Stevi-ns, O.B.E.,
j i'.I.C. Tuvlfih Edition.

1 COCOA AND CHOCOLATE: THEIR
; CHEMISTRY AND MANUFACTURE. By
1 R. WiiY.MPEii. Second Edition. 54 Illustra-

i lions,

I GENER.VL AND INDUSTRIAL CHEMIS-

1 TRY. By De. Ettore ]\Iolikaei. Second
English Edition. Translated bv T. H. Pope,

, B.Sc., F.I C.. A.C.G.I.

Inoi'fianic. 330 Iliustmtion.^.

Organic. Part 1 . 254 Illustrations.

' Part II. 303 Illustrations.

' QUANTITATIVE ORGANIC MICRO-

1 ANALYSIS. By F. Pregl, D.Sc., Pii.D.

I Translated from and German Edition b}’’ E.

FvLE:;.'iN, B.Sc., Fii.D. 42 Illustrations.

THE THEORY OF EMULSIONS ANT)
EMULSIFICATION. By W. Cl.\yton, D.Sc.,
F.I.e. 22 Illustrations.

ALLEN^S COMMERCIAL ORGANIC
ANALYSIS. New Edition (5th), Vols. 1 . — IX.
Edited by S. S. S.adtler, S.B., E. C.
L.ATHROP, A.B., Ph.D., and C. A. Mitchell,
:\I.A., F.I.e.

VILLAVEGCHIA’S APPLIED ANALYTICAL
CHEhllSTRY. Translated b}' T. H. Pope,
B.Sc., A.C.G.I. Vol. I. 58 Illustrations. 21s.
Vol. II. 105 Illustrations.

PARRY’S

G/YCLOP^DIA

i OF

A HANDBOOK

On the Raw Materials used by the Perrumcr, their
Origin,. Properties, Characters and Analysis ; and
on other subjects of Theoretical and Scientific
Interest to tiie User of Perfume Materials, and to
those who have to Examine and Value such Materials

ERNEST J. PARRY

B.Sc., F.I.C., F.C.S.
Analytical and Consulting Chemist

A — L

LONl^N

J. & A. CHUJRCHILL Ltd

104 GLOUCESTER PLACE
PORTMAN SQUARE
1925

P; lilted j}i Great Brifatii.

PREFACE

The need for a scientific ivork of reference devoted to perfumerv
and ds raw materials has long been felt, and it is hoped that the

publication of the present volumes will go some way towards
meeting that want.

Tormulai for finished perfumes are not dealt vnth. In the first
place, reaUy good formula! are rarely published, and the best of
those that are are merely an index to the perfumer, giving him
hmts as to the direction in which he should experiment. Wliere
such formula! are required they will be found to a more or less
unlimited extent in books of a more empirical character.

^ I have to express my great indebtedness to the folloiving publica-
tions and individuals for the kind way, in the case of the former
ui winch they have aUou'cd me to use them vlth a free hand, and’
in the case of the latter, for so Idndly contributing articles which’
will be found over them respective initials

The Perfumery and Essential Oil Record.

The Chemist and Druggist.

La Parfumerie Moderne.

Les Parfums de Fraiice.

Messrs. Roure-Bertrand Fils, Bulletin.

Messrs. Schimmel & Co., Reports.

C. T Boimett, B.So., P.I.O. (O.T.B .) ; M. Dowlmrst,

w M-So., P.I.e.

Sala-

M.C.

J JTT “taoyMge tto iindneas of Messrs. Scott, Greon-

The Chemstry of Essential Oils and Artiflciaf Perfumes ” the
copyright of which they own. , *

cr EENEST J. PARRY.

56a, Gbeat Dover Street,

London, S.E. 1.

ABIES OILS. — ^The oils usualty known as pine needle oils
include those obtained from various species of pinus, larix and
abies. (See under “ Pine bfeedle Oil.”)

ABSOLUTES. — ^The term “absolutes” is’ applied to the
most' highly concentrated form of floral perfumes which can be
made. There are numerous trade names for these highly-concen-
trated preparations, but they are, in the main, identical with, or
very similar to, the substances known commonly as absolutes.
The extraction of the perfume material of the plant by means of
a volatile solvent, which is afterwards recovered by distillation,
was used, in a more or less experimental manner, about the year
1835. Robiquet appears to be the earliest experimenter in this
du’ection, but it was due to Massignon and to Naudin to make
the process a commercial success. During the past tliirty years
the extraction has been carried out on a commercial scale. The
oily, waxy, and resinous matters of the plant are extracted from
the plant substance by means of the volatile solvent, leaving
behind the bulk of the inert and inodorous matter. The volatile
solvent, such as petroleum ether, is recovered by distillation,
generally under reduced pressure, in order to keep the temperature
as low as possible. The solvent must be able to dissolve the whole
of the odorous substances present, and must have no chemical
action on them. It should also dissolve as little as possible of
any inodorous substances. Eurther, it should boil at the lowest
possible temperature and leave no odour beliind when evaporated.
The semi-solid residue left behind on the evaporation of the
solvent consists of the odorous constituents of the plant, together
with the inodorous waxy matter. These substances are usually
known as “ concretes.” They are either sold as such (when the
perfumer has to filter ofi the matter insoluble in alcohol), or they
are further treated and converted into absolutes. This is effected
by treating them with alcohol in shaking machines, and the
alcohol is filtered. It is then exposed to a very low temperature
and dissolved wax is thus separated. The clear alcoholic solution

PEllFl'MEBY

i? now cither e^'aporated at a low temperature and the residue
sold as a)i absolute, or the perfume material is isolated by
salting out, when it can be separated, or it can be dissolved out
from the alcohol mixed vith brine, hy petroleum other, which is
then evaporated, and the residue is the absolute.

An absolute i.s understood to be a pure vegetable imoduct free
from the addition of synthetics, and it should form a clear
solution with alcohol, which ought not to precipitate on
cooling.

The^ solvent in almost general use to-day is a highly-purified
petroleum ether. >So far as any comparative figure can be given,
it ma 3 * be said that the concretes arc about forty times as strong
as the coiresponding pomades known as “ No. 3G,” and the
absolutes stronger still.

ACACIA.— This genus of the natural order LtguwwoscB
includes a number of plants with sweet-scented flowers. The two
of really cc mmerdal importance arc Acacia Farnesiana, which
yields the cassic perfume, and Acacia dcalhala, which, with several
other .species, \dclds the well-knomi mimosa perfume.

A small quantity’ of perfume is obtained for local use in
Austraha from various species of acacia known commonly as
wattle blossoms.

The perfume of the cassie flowers is veqy delicate, and is best
dealt with in the form of a pomade, but it is also made as an
absolute flower oil. It is wideN distributed over the warmer
districts of all continents. Tor example,^ it is found in EgjqDt,
Aiistralia, the Hawaiian Islands, the Philippine Islands, North
and South America, Prance, Algeria, Sjnia, northern India, and
New Caledonia. In Europe the collection of flowers commences
when the plants are three j-ears old. Each tree jdelds about
500 to GOO kg. of flowers, which are gathered twice weekly dui’ing
the months of September, October, and November, and sometimes
even in December. A good deal of pomade was at one time made
in India, but to-daj’- very little is manufactured there. In Sjuria,
near BajTCuth, the pomade is made, as the cassie tree is there
very plentiful. In the south of Prance the plant flourishes best
in the neighbourhood of Grasse and Cannes, vdierc it is knoum as
” cassie ancienne or “ casillier de Parnese.” A less odorous
species is Acacia cavenia, known as “ cassie romane.”

The principal flowering season is October-November, whilst in
favoura,ble seasons flowers are picked as late as January or-
Pebruary. Essential oil of cassie, a somewhat rare product, has

PERFUMER 7

a specific gravity 1-040 to 1-058 ; refractive index, 1-5130 to
1-5150 ; ester value, 114 to 230 ; and melts at about 18°. It
contains farnesol, geraniol, linalol, benzaldebyde, eugenol, benzyl
alcohol, methyl saHcylate, decylic aldehyde, cuminic aldehyde,
anisic aldehyde, para-cresol, and a ketone of violet colour.

The essential oil from Acacia cavenia contains eugenol, methyl
salicylate, benzaldehyde, benzyl alcohol, anisic aldehyde, eugenol
methyl ether, and a ketone with a violet odour. Linalol and
decylic aldehyde are also probably present.

Cassie, either in the form of a pomade, concrete, or absolute, is
of great value in the preparation of violet bouquets. Synthetic
cassie perfumes can be, and are, manufactmed on the basis of the
composition of the essential oil given above, assisted by the
judicious use of traces of the higher fatty aldehydes, especially the
12 carbon aldehyde, a small quantity of one or other of the
ionone ketones, and para-methyl acetophenone.

Acacia dealbata {Mimosa dealbata) is the principal tree whose
flowers are used for the preparation of the mimosa perfume, in
the same way as the cassie perfume. The crop is gathered from
February to March. Acacia fioribimda is also used for the perfume.
Artificial mimosa resembles artificial cassie, and methyl-aceto-
phenone and its homologues are used in its preparation, together
with methyl-heptin-carbonate and hydroxycitronellal.

The oil from Robinia pseudacacia is of good odour value, but is
scarcely a commercial article. The flowers are sometimes made
into a concrete or absolute flower oil, which has a typical acacia
odour. The essential oil has a specific gravity 1-05, and contains
linalol, a-terpineol, benzyl alcohol, indol, and heliotropin (Elze,
Cham. Zeit., 34, 814).

(For an account of other species, see Les Parfitmes de France,
1924, 13, 35.)

ACETEUGENOL. — ^This body, is a crystalline

compound formed by the action of acetic anhydride on eugenol.
It melts at 29°. It is present to a very small extent in oil of
cloves.

ACETIC ACID. — Solutions of acetic acid are employed in
•the manufacture of toilet vinegars. It should be pure, water-
white, and free from the slightest enipyreumatic odour. It is an
acid obtained by the distillation of wood (also synthetically), and
has the formula CHgOOOH. The following table gives the most
useful strengths as determined by the specific gravity, which.

P E P r V M E B Y

wiicic u specific jiraviiy ovei’ 1*050 is being clefilt with, must be
ciiecived by titration : —

Sp. gr.

Percent. |

Sp. gr.

Per cent.

1-000

1-065

1-007

1-068

1*014

1-071

1-021

1-073

i-028

1-075

1-035

1-075

1-041

1-074

1-047

1-071

1-052

' 1-066

1-057

1-055

100

1-061

AGETIN. — The term acelin is used to include the three acetic
esters of glvcerin. mono-, di-. and in- acetin. A mixture of these
is used as an adulterant of essential oils, but, being much more
soluble in water than the natural esters, may readity be detected
bv washing two or three times witli hot water, and noting anj
decrease in volume of the oil. The acetins are used to some
extent as solvents for essential oils, either alone or in conjunction
vith alcohol ; they are miscible iii all proportions with 20 under
proof spirit. {Vide ‘'Artificial Esters.' )

ACETON APHTHONE .—This body, a-naphthyl-methyl ketone
C10H7.CO.CH3, is prepared by condensing naphthalene and acetyl
chloride with the assistance of aluminium chloride. It is best
condensed in monochlor-benzene solution (Chopin, French patent
530,257). It has a very useful orange-blossom odour, and is useful
in admixture with phcnyl-etlnd alcohol and methyl anthranilate
in the preparation of art.ificial neroli oils. It forms crystals
melting at 34°, and boils at 295°.

ACETOPHENONE.— This ketoire, CcH5.CO.CH3, occurs
iiaturallj’’ in oil of ladanuin resin, and in the oil of an Australian
plant, Slirlmgia laiifolia. of which it forms about 90 per cent.

It has a persistent and powerful odour, which is taken advantage
of by perfumers in the preparation of perfumes of the type of
new-mown hay, s^sninga, and the lilce.

It is prepared artificially by pouring acetyl chloride slowly on
to a mixture of benzene and aluminium clrloride at a lov' tempera-
ture. Hydrochloric acid is evolved, and the product is left for
several hours at ice temperat'ure. It is then washed with water,
then vith dilute advali, and rectified mi vacuo. Its oxime melts
at 59°.

•t

PEBFUMEB Y

Acetophenone is a crystalline substance melting at 19° to 20°, and
boiling at 200° to 202°, It has a specific gravity 1-033, and refractive
index 1-5355. It is used medicinally under the name “ Hypnone.”

ACETYLATION. — See “ Alcohols, Determination of.”

ACHASMA WALANG, OILS OF.— The essential oils have
been extracted separately from the leaves, the stems, and the
roots of this member of the Zingiber acece, Achasma Walang Val.,
or Amomum Walang Bl., which in’ Java goes under the name of
daon walang.

JRoiire-Bertrand Fils {Bulletin, April, 1914:, 154) give the follow-
ing characters of the oils : —

Oil of the Leaves (yield, 0-25 per cent.)

Specific gravity .... ,0-850

Acid value ..... 10-1

Optical rotation . . . . —0° 34'

Saponification value . . .70

Aldehj^des (neutral sulphite method) . 97 per cent.

Oil of the Steins (yield, 0-2 per cent.)

Specific gravity . . . , 0-860

Acid value ..... 26

Optical rotation .... —0° 58'

Saponification value . . .75-6

Saponification value after acetylation 285-6
Aldehydes 96 per cent.

Oil of the Boots (yield, 0-15 per cent.)

Specific gravity .... 0-856

Acid value .’.... 18-9

Optical rotation .... —0° 30'

Saponification value ... 70

Saponification value after acetylation 285-6
Aldehydes 96 per cent.

ACHILLEA M OS CHAT A. — ^This plant, known as the musk-
scented milfoil, is found on the Alps at an elevation of 5,000 to
10,000 feet. On distfilation of its flowers and leaves it yields an
essential oil which has been used to perfume the Swiss liqueur
known as Iva. It contains cineol, valeric aldehyde, Zceyo-camphor,
palmitic acid, and an oxygenated body termed ivaol, of the
formula C24H4o02- The pure oil has a specific gravity 0-928
to 0-960 ; optical rotation, — 12° to — 15° ; refractive index,
1-4760 ; and ester value, 18 to 44.

ACOR.US CALAMUS. — ^This plant, commonly known as
the sweet flag, is a member of a genus of semi-aquatic plants

PERFUMER Y

belonging to the natural order Aroidce. It must not be confounded
with the Indian “ calamus aromaticus/' which is now recognised
as one of the Andropogon family. Acorns calciums grows best by
the banl'is of rivers and in marshy ground, being plentiful by the
rivers in Norfolk. It is now cultivated in damp marshy places in
India and Burmah. In warm climates it develops greater fragrance
than it does in England. From the lower part of the thick, jointed
rliizome the plants send down numerous long, slender roots, but
it is from the rhizome itself that the essential oil is distilled.

The dried rhizome is found in commerce as flattened pieces
from 4 to G inches long and about -jj inch thick. It is of a yellowish
brovai or favm colour externally. In India the rhizome is used in
the preparation of an aromatic vinegar. In Europe the rhizome is
used in the form of powder as a constituent of toilet and sachet
powders, but its use has decreased of late years.

According to Russell (Jonr. Amer. Clicm. Soc., 1915, 37, 2387),
aU parts of the plant contain an essential oil, which varies in
characters with the portion of the plant from which it is
obtained.

The normal essential oil of sweet flag, which is used to some
extent as a perfume material, and also as an ingredient in the
flavour of gin and some types of beer, is distilled from the
rhizomes. Its specific gravity varies from 0-950 to 0-970 ; optical
rotation, 9° to -- 35'" ; refractive index, 1-5000 to 1-5080 ; and
ester value from 5 to 20.

It contains pincnc. camphenc, camphor, a sesquiterpene termed
calamcnc, a sesquiterpene alcohol, eiigcnol, hcptylic acid, palmitic
acid, and asarvlic aldehvde.

There is a Japanese calamus oil, distilled from Calavuis sgjuxius.
which diflers somewhat from the oil from C. aromaiicus, but
resembles it in general characters.

AFRICAN COPAIBA OIL. — Sec “ Hardwickia Balsams."

AGLAIA FLOWERS. — ^The flowers of AgJaici odoraia,
known locally as Lan-hva or Yn-chv-Ian, arc used by the Chinese
for the purpose of scenting tea.

AJOWAN SEED OIL. — Ajowan seed is the fruit of Ptychotis
Ajoivaii {Carinn Ajouxai, Garum cojMcwn), u plant known as

true bishop’s^ weed. ' The plant is cultivated in many parts
of Egjpt, Persia, Afghanistan, and Bengal. It is indigenous to
India. The seed yields from 3 to 4 per cent, of essential oil,
having a powej-ful odour of thymol. In addition to its principal

()

PERFUMERY

constituent, .tliymol, the oil contains cymene, pinene, dipentene,
and terpinene. The oil is used on a large scale for the preparation
of thymol {q.v.). In the native bazaars of India the oil is allowed
to evaporate^ spontaneously, and the crude thymol is sold under
the name Ajivain-ha~pliul (Flowers of Ajowan). The odour of
the oil is pungently aromatic. The plant is known by the following
vernacular names in the East : —

Arabic .
Persian .
Hindustani
Duldini .
Tamil
Telegu .
Malaylim
Canarese
Bengali ' .
Mahratta
Gujerati
Burmese

Kamune-muhihi.

Nanhhah and Zinyan.
Ajvayan.

Ajvan.

Omani.

Omamu or Vamamu.
Ayamodaham and Eomam.
Varna.

Ajvain or Ajvan.
Vova-sada and Vova.
Ajioan.

Samhum.

Experimental cultivations have been started in the West Indies,
but so far they have not 3 delded commercially successful results.

The essential oil has a specific gravity 0*910 to 0*930 ; optical
rotation, -{-.1° to + 5° ; and refractive index, 1*4980 to 1*5005.
It contains from 45 to 60 per cent, of thymol, and serves as a raw
material for the extraction of this important bod 3 ^

Bodh Baj Sobti and Puran Singh (P. ds E. 0. R., 1923, 399)
state that in the thymol manufactory of the Scindia Chemical
Laboratories, Gwalior, they found a large fraction of a dark
residual oil which would not crystallise at aU— left as it was after
the whole of the thymol was crystallised out from the phenol
fraction of the ajowan oil wliich was obtained by shaldng the oil
with caustic soda solution. It seemed interesting to identify
this material, especially when the presence of carvacrol in ajowan
oil had yet to be confirmed. {Vide Parrjr, “The Chemistry of
Essential Oils,” 3rd edition, vol. i., p. 303.)

Large quantities of this fraction of the phenols were available
in the thymol refinery. After repeated distillation and refrigera-
tion, these gave sufficient quantities of a non-crystallising phenol
distilling over between 236° and 240° C. at 746 mm. pressure. It
had the following physical constants : —

Specific gravity at 29*0° C. ’ . 0*9712

Optical rotation . . .0

Refractive index at 28° . . 1*5230

7 "

PEBF UMER Y

r c

Oil combustion found |

{ c

Theoretical CioHi.jO |

SOTO per cent.
9-38
SO-00
9-33

Tliere are a good number of phenols of the formula OiqHi.iO
n'hieh have their boiling points near 235° 0. In order to eliminate
some of these, tlie methyl ether was prepared.

There are four possible isomeric methyl ethers which have their
boiling points near 21G° C., viz.

(1) Meth}-! ether of 4-oxy-3-in-opyl-l-methyl benzene, boiling

point 210° to 218° C.

(2) IMothyl ether of O-oxy-S-isopropjd-l-meth^d benzene, boiling

point 217° C.

(3) Method ether of 2-ox3'-4-isopropyl- 1-methyl benzene (carva-

croi), boiling point 216-8° C.

(4) Methyl ether" of 3-oxy-4-isopropyl-l-mcthyl benzene (thy-

mol), boiling pomt 210-20° C.

Fm-ther. the metiiyl ether, on oxidation with 5 per cent,
potassium permanganate in alkaline solution, gives an oxymethyl-
dicarboxylic acid hamng a definite melting point. It was prepared
as follows : —

The methyl ether was suspended m strong sodium carbonate
solution and kept ice cold. Five per cent, potassium permanganate
solution (the calculated quantity) was added in portions until the
coloui’ was slightly permanent. To destroj’’ this, a little alcohol
was added. Manganese dioxide was filtered off and washed with
hot water. The filtrate was taken donm to a small volume on a
water bath, and then acidified with hydrochloric acid. The
methoxy acid thus obtained was recrystallised from • alcohol.
Its melting point was 277° C.

J^Iethyl ether of 4-oxy-3-prop3d-l-methyl benzene and 6-oxy-3-iso-
propjd-l-metlijd benzene give the same oxy-meth3d-dicarboxylic
acid melting point 201° C ; while ineth3d ethers of 2-oxy-4-iso-
prop3d-l-meth3d benzene (car vacrol and 3-oxy-4-isoprop3d-l-meth3d
benzene (th3-mol) give the same ox3nneth3’'-dicarbox3dic acid which
melts at 277° C. Therefore, the phenol under investigation can be
either th3miol or carvacrol.

A drop of ferric chloride was added to an alkaline solution of
this phenol ; it was coloured green, and after some time changed
to a dark brown colour. This led the authors to ‘suspect the
presence of carvacrol. This was further confirmed b3'' the colour
produced b3' heating it vith formaldeltydc (Hermann Bndermann,

PE EF.UMB El

Jour. Soc. Ghem. Ind., 1896, 791-792). A little of tlie substance
Avas dissolred in commercial formalin, the solution evaporated
nearl}’’ to dryness at a low temperature, and concentrated sulphuric
acid added. The solid residue was coloured orange. To be sure
of the colom’ reactions, a little pure thymol and carvacrol were
treated under similar conditions. Tlie colour produced by the
caiwacrol sample was exactly similar to that produced by the
fraction under investigation. For furtlier confirmation, the nitroso
compmmd was prepared, the melting point of wliich was 153° C.

ALCOHOL. — ^Alcohol is the most important substance used
by- the perfumer. So many^ of the substances used in perfumery
are only soluble in organic solvents, that water is of comparatively’'
little use. The solvent for the perfumer must be very volatile,
and must be sufficiently free from odour not to interfere with the
perfume value of the ingredients dissolved therein. - Prolonged
experience has demonstrated the fact that alcohol is the best
solvent which meets the general requhements of the perfumer.
There are other solvents, such as isopropyd alcohol (q.v.), which
are of considerable use, but there is no other that will effectively^
replace ordinary alcohol without so7nc disadvantage.

Alcohol, or ethyl alcohol, is a substance which is obtained
universally by fermentation processes. It results from the
decomposition of sugar by means of the y-east organism, which
breaks sugar dovm into alcohol and various other secondary’
constituents. For the perfumer it is of the highest importance
that the alcohol employed should be as free as possible from such
secondary constituents, and have as little odour as possible. In
this country’ the alcohol generally’ preferred is grain spirit, Avliich
is as free from secondary’ constituents as possible.

Pure or absolute alcohol, that is, alcohol of 100 per cent,
strength, C 2 H 5 OH, is a colourless volatile liquid of faint, delicate
odom’, having a specific gravity 0-794 at 15-5°, and boiling at 7S°
to 79°.

The perfumer rarely’ uses alcohol of this strength, as, of course,
the duty on alcohol in this country is exceedingly high. His aim
is, therefore, to use the lowest strength alcohol possible com-
patible ■with efficiency in his products. That efficiency demands
that the necessary ingredients shall be perfectly soluble, and that
the finished product shall be sufficiently volatile. The considera-
tions that arise, then, are : firstly, the determination of the
strength of the alcohol to be used ; secondly, the tests necessary
to detect impurities in the alcohol ; and thirdly, as is veiy fre-

PE BFIJ ME B Y

quently necessary, the estimation of tiie alcohol in the finished
product.

(1) For all practical purposes the perfumer can rely on the
specific gravity of the alcohol as a correct measure of its strength.
This is true if it he mi.vod with nothing else but water ; otherwise
it is not true, and the innscnce of foreign substances must be
allowed for.

A term frequently used is proof spirit, together with the
expression “ degrees under or over proof.” The term iwoof
spirit had its origin einpii’ically. The excise ofiiccrs in early days
tested alcohol for duty purposes by pouring a given amount on
a given weight of gun])owder. If it Avas below a certain strength,
the gunpowder did not ignite on the application of a light ; if
above a certain (empirical) strength, it did ignite. Hence the
terms under or over proof. To-day, proof spirit is legally defined
as alcohol of such a strength that, at 51°, 13 volumes shall weigh
as much as 12 volumes of Avatcr.

Proof spirit has a specific gi’aAuty at 15-5° C., 0-910S, and
contains 45'-2S per cent, of alcohol by AA-cight, or 57-] per cent, by
A'olumc. The expressions Ainder or oA'er joroof mean as follows.
Ii a samjfie of alcohol contains as inuch alcohol as corresponds
AA-ith SO per cent, of proof strength, it is 20° vndcr proof. If it
eontains alcohol corresponding AA'itli ] 20 per cent, of proof strength,
it is 20° o?-c?' proof. The folloAA'ing table gives the strength of
mixtures of aleohol and Avatcr by volume. Tlieso figures arc from
the table in use in the GoA-ernment labor.atoiy : —

Specific
cravitv ,

Ab-oliii''

.Vlt'Oim. ;

rorc^nla"'?

Broof

Spirit.

III GO r.

(i:r,v C.)

volume.

v/elpht. !

1000

O'OO

0-00

999 1

0-6G

0-53

998

1-3-L

1-07 1

i 2-33

997

2 02

TGI

1 3-52

99G '

‘ 2-71

2-17 I

1'73

99-5

3-12

2’73 1

1 0-98

991 '

1-M

3-31 !

' 7-2-1

993 i

1-88

3-90

8-51

992 !

5-03

4-51

i 9-82

991 '

G-10

5-13

IMG

990 1

7-] 8

U-7G

12>53

989 1

7-93

OAl

13-94

988 '
1

8-80 ’

: 7-08

15-38

Specific
jirnvitv
nt 00' 1 \
(Lfr.V C.)

Alj'olutc

Alcohol.

rcrceut.'\"o

Proof

Spirit.

volume.

\vcipht .

987

9-G5

7-7G

16-85

986

10-51

8-lG

18-34

985

11-40

9-18

19-87

984

]2-29

9-91

21-44

983

13-20

10-65

23-02

982

i 14-13

11-12

21-66

981

15-08

12-20

26-32

980

lG-04

12-99

! 27-99

979

17-02

13-80

29-70

978

18-00

14-61

31-42

977

18-99

15-43

33-15

976

19-98

16-25

31-87

975

20-97

17-08

36-61

PEE FV ME BY

Specific
gravltv
nt 00'' r,
(15*5® C.)

j Altsoluto Alcohol.

Percontnee

Proof

Spirit.

volume.

weight.

974

21-96

17-90

38-35

973

22-94

18-72

40-06

972

23-91

19-53

41-77

971

24-85

20-34

43-47

970

25-83

21-14

45-14

969

26-77

21-93

46-77

968

27-69

22-71

48-38

967

28-69

23-48

49-98

966

29-18

21-23

51-53

965

30-34

21-97

53-04

964

31-18

25-68

54-51

963

31-99

26-37

55-93

962

32-79

27-06

67-33

961

33-56

27-73

58-68

960

34-33

28-39

60-03

959

35-06

29-03

61-32

958 '

35-79

29-66

62-60

957

36-50

30-28

63-85

956

37-20

30-90

65-09

955

37-89

31-50

66-29

954

38-57

32-09

67-48

953

39-22

32-67

68-62

952

39-87

33-25

69-76

951

40-50

! 33-81 i

70-87

950

41-13

34-37 i

71-98

949

41-74

34-92

/ 3 -OiJ

948

42-35

35-46

74-12

947

42-95

36-00

75-17

946

43-54

36-54

76-21

945

44-13

37-07

77-24

944

44-71

37-60

78-26

943

45-28

38-12

79-26

942

45-85

38-64

80-26

941

46-40

39-15

81-23

940

46-95

39-65

82-19

939

47-50

40-15

83-15

938

48-04

40-65

84-10

937

48-57 i

41-15

85-01

936

49-10

41-64

85-97

935

49-63

42-13

86-89

934

50-15

42-62

87-81

933

50-67

43-11

88-71

932

51-18

43-59

89-61

931

51-68

44-06

90-49

930

52-18

44-53

91-36

929

52-67

45-00

92-23

Specific
gravity
at CO’ i'.

(15-5° C.)

Absolute

Alcohol.

Percentago

Proof

Spirit.

volume.

weight.

928

53-16

45-47

93-09

927

53-65

45-94

93-95

926

5 - 1-14

46-40

94-80

925

54-62

46-87

95-65

924 .

55-10

47-33

96-49

923

55-58

47-79

97-33

922

56*05

48-25

98-16

921

56-52

48-71

98-98

920

56-99

49-17

99-80

91976

57*10

49-28

100-00

919

57-16

49-63

100-62

918

57-92

50-08

101-43

917

58-38

50-53

102-24

916

58-83

50-98

103-05

915

69-29

51-43

103-84

914

59-74

51-88

101-63

913

60-19 •

52-33

105-42

912

60-63

52-77

106-20

911

61-07

53-21

106-97

910

61-51

53-65

107-74

909

61-95

51-10

108-52

908

; 62-39

54-51

109-29

907

: 62-83

54-98

110-06

906

63-26

55-42

110-82

905

63-70

55-87

111-59

904

64-13

56-31

112-35

903

64-56

56-75

113-10

902

64-98

57-18

113-84

901

65-41

57-62

114-59

900

65-83

58-06

115-33

899

66-25

58-50

116-07

898

66-67

58-93

116-81

897

67-08

59-37

117-54

896

67-50

59-80

118-26

895

67-92

60-23

118-98

894

68-33

60-66

119-70

893

68-74

61-09

120-42

892

69-14

61-52

121-14

891

69-55

61-95

121-85

890

69-95

62-38

122-56

889

70-35

61-81

123-27

888

70-75

63-24

123-97

887

71-15

63-67

124-06

886

71-55

64-10

125-37

885

71-95

64-53

126-07

PERFUMERY

Specific 1

Absolute AlcolioL

•j

Percentage

Proof

Spirit,

Specific
gravitv
at 00"' P.
(15-5= C.)

Absolute Alcohol.

Percentage

Proof

Spirit.

nt ro^ r.
{15‘5= C,)

volume, ]

weight,

volume.

weight.

884 i

72-34 ;

64-96

126-77

838

88-68

83-99

155-47

883 ,

72-74 1

63-39

127-46

837

88-99

84-39

882

73-13 ,

65-81

128-14

836

89-30

84-78

156-56

881

73-52 '

66-24

128-82

835

89-61

85-17

157-10

880

73-91 *

66-66

129-50

834

89-91

85-56

167-63

879 >

74-30 •

67-09

130-18

833

90-22

85-95

158-16

878

74-68

67-51

130-86

832

90-52

86-34

158-68

877

75-06 !

67-93

131-53

831

90-82

86-73

159-21

876

75-44 1

68-35

132-19

830

91-11

87-11

159-73

875 '

75-82 1

68-77

132-86

829

91-40

874 ,

76-19 1

69-19

133-53

828

91-69

■iHUffn

873 ■

76-57 ;

69-62

134-19

827

91-98

88-27

161-26

872 '

76-94 :

70-04

134-84

826

92-26

161-76

871

77*32 1

70-46

135-50

S 2 d

92-55

162-26

870

77-69

70-88

136-16

824

92-83

89-41

869

78-06

71-30

136-83

823

93-11

89-79

868

78-43

71-72

137-46

822

93-38

867

78-80

72-34

138-10

821

93-65

866

79-17 '

72-53

138-74

820

93-92

164-67

865 '

79-53

72-97

139-38

819

94-19

91-27

165-14

864

79-89

73-39

140-02

818

94-45

91-63

863

80-25

73-81

140-65

817 !

9 - 1-71

166-06

862

80-61

74-22

141 - 28 -

1 816

94-97

92-36

166-51

861

80-97 1

74-64

1 - 11-91

' 815

95-22

92-72

166-96

860 !

81-32 1

75-05

142-54

814

95-47

167-41

859 1

81-68 !

75-47

143-16

813

95-72

93-44

167-86

858 1

82-03 ;

75-88

143-78

812

95-97

93-80

857 1

82-38 !

! 76-30

144-40

811

96-21

94-15

168-71

856 :

82-73 ’

' 76-71

145-01

810

96-46

169-13

855 '

83-08

j 77-12

145-62

809

96-69

854

83-42

! 77-53

146-23

808

96-93

169-96

853 '

83-77

' 77-94

146-83

807

97-16

95-55

170-37

852 i

84-11

I 78-35

147-43

806

97-39

95-89

851 i

84-44

' 78-76

148-03

805

97-62

96-23

171-17

850 1

84-78

i 79-17

148-62

804

97-84

171-56

849 1

85-12

1 79-58

149-21

803

98-06

96-91

171-95

848 ’

85-46

i 79-98

149-80

802

98-28

97-25

172-23

847 .

85-80

' 80-39

150-39

801

98-49

97-59

172-71

846

86-12

80-79

150-97

800

98-70

97-91

173-07

845 ■

86-44

81-20

151-55

799

98-91

98-24

173-44

844

86-77

81-60

152-12

798

99-12

98-57

843 ;

87-09

82-00

152-68

797

99-32

174-16

842 i

87-42

82-40

153-25

796

99-52

99-22 -

174-52

841 !

87-74

82-80

153-81

795

99-72

99-55

174-87

840

88-06

83-20

154-37

794

99-92

175-21

839

88-37

83-60

154-92

79359

' 100-00

175-35

PEBFU MElli’

(2) Detection of Impurities . — ^The impurities in alcohol will
depend to a large extent on the source of the saccharine solution
by the fermentation of which the alcohol is obtained. In England,
grain starch is the principal soiirce of alcohol ; in France it is
vciy largely beet sugar ; in Germany, potato starch ; and in the
United States maize is emplo5’'ed to a very large extent. Rice
flour is used considerably in Eastern countries. Grain spirit and
beet sugar sphit are usually most valued, as they contain less of
the objectionable impurities which tend to spoil the odour of
perfumes.

The principal impurities to bo guarded against, apart from delibe-
I'ate additions such as appreciable quantities of methyl or isopropyl
alcohols, arc aldehydes, esters, and the higher alcohols. These
bodies, associated in different proportions in alcohols having
different origins, are general^ described under the name fusel oil.
These impurities are largely removed by diluting the alcohol with
water, when a certain amount of the impurities are thrown out of
solution, and may be separated, the alcohol being then again
concentrated by fractional distillation, the first runnings and the
tailmgs being rejected for retreatment, the middle runnings being
almost pure alcohol, mixed with a little water. For very special
purposes, alcohol (rectified spiiit, sphit of wine) may be still
further pmified by treatment with chemicals such as silver
nitrate, to decompose the last traces of aldehyde, and again
distilling. Such highly purified alcohol is often Icnowm as Cologne
sphit, and is suitable for use in the most delicate perfumes.

The following test, originally due to MuUilven and Scudder, will
detect as little as 2 per cent, of methyl alcohol in ethyl alcohol.
One cubic centimetre of the sample is diluted to 10 c.c. with
water, or, if already dilute, to about 10 per cent, strength. A
copiDcr wire sphal is made by winding 1 metre of copper wire,
about No. 18 gauge, round a glass rod 7 mm. thick, making a
coil 30 mm. long, the remaining portion of the wire being used as
a handle. The coil is heated to redness in a bunsen flame, and at
once immersed in the liquid contained in a test-tube. This is
repeated five or six times, the- tube being kept in cold water in
order to prevent the temperature rising too much. . The liquid is
filtered into a wide test-tube and boiled very gently. If an odour
of acetaldehyde is perceived, the boiling is continued until it has
disappeared. The liquid is now cooled, and a drop of a O' 6 per
cent, solution of resorcin is added. A portion of the liquid is then '
carefully floated on to strong sulphmic acid, allowed to stand, and

PKiRFUMEB y

then gently rotated. If a rose red-ring ap23ears at the contact zone,
methyl alcohol is not present to the extent of more than 2 per
cent. — a most unlikely quantity for anj”" deliberate adulteration.

Having determined the strength of the alcohol and the absence
of methjd alcohol, the following determinations are, if deemed
necessary, made ; —

(а) Total Solid Bcsiclue . — If 50 c.c. be evaporated on a water
bath, the solid residue should be so slight as to be unweighable.

(б) Free Acids . — If a few drops of phenoljDhthalcin be added to
•50 c.c. of the alcohol, 0-2 c.c. of decinorraal barj^ta solution should
cause a jhnlc colour to develop. A good i^erfume spuit should
contain less than 3 parts j^er 100,000 (calculated as absolute
alcohol) of free acids calculated as acetic acid.

(c) Total Aldehydes . — The best j)rocess for the determination of
the aldeh 3 'des is the official 2 )rocess of the French Government.
This is carried out as follows. A standard solution of 0-1 gram
of aldeh 3 ’de per litre Is made b 3 ’’ dissolving 1*386 grams of aldeh 3 ’de
ammonia crystals (= 1 gram of aldeln'de) in about 50 c.c. of jjure
95 per cent, alcohol. 22*7 c.c. of normal sulphuric acid solution
are added, when ammonium sulphate is precipitated. The liquid
is made up to 100 c.c. vith 95 per cent, alcohol, and another 0*8 c.c.
is added to compensate for the precipitated ammonium sulphate.
The liquid is left for twelve hours, after being ■well shaken, and
filtered. About 90 c.c. of water are added, and the whole diluted
to 1 litre with 50 i^er cent, alcohol. This is now practicall 3 ’’ a
50 per cent, alcoholic solution, and when diluted ten times with
50 per cent, alcohol, is a solution containing 0*1 gram of aldeltyde
]ocr litre, or 1 in 10,000.

A fuch sine-sulphurous acid solution is prej^ared b 3 ’ mixing 30 c.c.
of a 0*1 per cent, solution of fuchsine in 95 per cent, alcohol,
15 c.c. of a solution of sodium bisulphite in water (specific gravity
= 1-30S), and 30 c.c. of water. The mixtiu’c is shaken and
allowed to stand for an hour. Fifteen cubic centimetres of
30 per cent, sulphuric acid are then added, and the liquid made
up to 250 c.c. vith 50 per cent, alcohol.

The sample to be tested is diluted vith water to 50 per cent,
strength and 10 c.c. of the standard solution is treated Avith 4 c.c.,
of the fuchsine -sulphurous acid solution, and the colour developed
is matched by adding 4 c.c. of the fuchsme-sulphurous acid solution
to sufficient of the diluted sample. From the amount used the
quantity of aldeh 3 ’-des is calculated, and should be returned in
parts per 100,000 of absolute alcohol. Ver}’’ fine samples contain

PERFUMERY

less than 1 part, and should not contain more than about 2-5 to
3‘5 parts per 100,000 of absolute alcohol.

{d) Esters . — The aldehydes are first removed by boiling for an
hour -with 3 per cent; of metaphenylene diamine under a reflux
condenser. The liquid is then distfiled, 90 per cent, being collected,
and the distfilate made up to its original volume. The esters are
now determined by saponification in the usual manner, and are
returned as parts of ethyl acetate per 100,000 of absolute alcohol.
Crude grain spirit may contain 20 to 50 parts per 100,000, but the
finest samples will contain only 4 to 10 parts.

(e) Higher Alcohols . — ^There is no exact method of carryuig out
this determination, but Marquardt’s process, modified by Allen
and Schridowitz {Jour. 8oc. Chem. Ind., 1902, 815), probably gives
the best results obtainable. Two hundred cubic centimetres of
the alcohol are boiled under a reflux condenser with 0-2 gram of
KOH for one hour, and the liquid distfiled until 180 c.c. have
passed over. Steam is passed through the' residue until 300 c.c.
are collected. The alcoholic strength should be as near 50 per cent,
as possible, either by the addition of pure alcohol or water, iE and
as necessary. The exact vqlume is noted, and 100 c.c. taken for
the distillation. This is mixed with saturated brine until the
specific gravit}’- is 1-100. The liquid is then extracted with three
successive quantities of carbon tetrachloride of extreme purity,
the separated carbon tetraclfioride shaken with a 50 per cent,
solution of potassium sulphate, and finally separated and filtered.
It is then oxidised by a solution of 5 gr. of potassium biclmomate,
2 gr. of sulphuric acid, and 10 c.c. of water on a water bath
for eight hours, under an ejEficient condenser. The liquid is
distfiled, firstly over a bunsen burner, and then with steam, until
about 300 c.c. have been collected. The carbon tetrachloride is
separated and washed with^water, the washings being added to
the aqueous distillate. This is then titrated with decinormal
baryta, using phenolphthalein as indicator, after traces of mineral
acid have first been neutralised to methyl orange. It is usual to
return the higher alcohols calculated as amyl alcohol, so that the
acids so found are calculated to valerianic acid. Each cubic
centimetre of decinormal allrali is equivalent to 0-0088 gram of
amyl alcohol (or 0-0074 gram of butyl alcohol). Calculated to
100,000 parts of absolute alcohol, the best perfumery spuit should
contain less than 10 parts, sometimes as low as 3 parts, per
100,000.

Finally, it is often necessary to determine the strength of mixed

PEBFVMEBY

perfumes in alcohol when the specific gravity is useless, owing to
the presence of essential oils, etc. The following process (Thorpe
and Holmes, Jour. Cliem. Soc., l'903, 83, 314) may he used.
Care should he taken that all measurements, etc., are made at
exactly 15-.5°. Twenty-five cubic centimetres of the sample are
mixed with about 125 c.c. of water, and the whole saturated with
salt in a separator. The mixture is extracted twice with from
50 to 80 c.c. of petroleum ether, the mixed petroleum extracts
washed tvice •with brine, and the washings added to the original
liquid. The Hquid is distilled until all the alcohol has passed over,
and the distillate diluted to 100 c.c. and its specific gravity taken.
From this the amount of alcohol is found, and multiplied by 4
gives the percentage in the original sample.

(For further details, see E. J. Parry, “ Food an^ Drugs,” vol. i.,
Scott, Greenwood & Co,, London.)

ALCOHOLS. — ^The group of bodies kno'Rm under the generic
name ” alcohols ” play a very important part in the art of
perfumery, both from the natural and the synthetic points of
■^dew. The alcohols may, for general purposes, be described as
bodies contaming one or more hydroxyl (OH) groups, which are
characterised bj’’ then’ ability by reactions "with acids to exchange
themselves for acid residues, and so give rise to esters correspond-
ing with salts of mineral acids. Thej’- are distinguished from the
phenols — bodies belonging entirely to the closed-chain group of
compounds — where one or more of the hydrogen atoms of the
ring have been substituted by OH groupsr The phenols are
sharpty differentiated from the alcohols by their acid nature, on
account of "s^hich they readily combine •Rntli aUcalis to form alkaline
phenolates.

Alcohols are termed monohj^dric, dihydric, etc., according to
the number of hydi'oxyl groups they contain. Thus ordmary
“ alcohol,” or, more properly, ethyl alcohol CgHg.OH, is a"
monohydric alcohol ; ethjdene gtycol CoH4(OH)2 is a dili5rfric
alcohol ; glycerine C3H5(OH)3 is a triliydiic alcohol, etc., etc.
The monohydric alcohols are the most important of those which
are found naturally in perfume materials, and of those which are
manufactured artificially. They are sub-divided into three well-
marked groups ; these are the primary, secondary, and tertiary
alcohols.

The primal}^ alcohols are characterised by the hydrogen being
linked by. bivalent oxygen to a univalent radical. Thus geraniol,
(CioHj^^)' — 0 — ^H has the univalent radical (G10H17)' linlced to

PERFUMER Y

the hydrogen atom of the hydroxyl group by the bivalent atom
of oxj^gen. The primary alcohols are characterised by being
oxidised (generally) with the formation of aldehydes containing
the COH group, “and thence to acids containing the CO OH group.
In primary alcohols, therefore, the OH group is attached to a
— CHg — group.

In secondary alcohols the OH group is attached to a bivalent

/T? f

radical thus, H.O — 0E[\^ , "sphere R and represent other

radicals attached to the linking carbon atom. Thus isopropyl

alcohol, wliich may be represented by the formula OH,

is a secondary alcohol. They are characterised by not yielding
aldehydes on oxidation, but ketones containing the — CO — group.
Finally, where the hydrogen is linlced up to a trivalent radicle,

thus, H — 0 — C;^R' , the alcohol is termed tertiary. These

alcohols 3 deld neither aldehydes nor ketones on oxidation, but are

/CHg

decomposed by the process. Trimethyl carbinol H.O.C^CHg is

^CHg

an example of a tertiary alcohol.

The principal alcohols found naturally in essential oils, or manu-
factured artificially for perfumery purposes, are monohydric and
primary. They exist to a considerable extent in the free state,
such as geraniol in palmarosa oil, and also in the form of esters,
such as geraniol as geranyl tiglate in geranium oil, and linalol as
Knalyl acetate in bergamot and lavender oils. The more im-
portant of these will be found described under their particular
name, and methods for their determination will be found under
the headings'” Alcohols, Determination of,” and “ Esters.”

The alcohols soluble in water are not, except possibly in minute
ti’aces, to be found in distilled essential oils, as they have, of course,
if present, been dissolved 'out in the distillation waters. The
alcohols present in essential oils are either the open-chain alcohols,
such as the alcohols usually classed as " fatty alcohols ” and those
sometimes classified, as a matter of convenience, as the open-chain
“ terpene ” alcohols of which geraniol is the type ; or they are
the closed-chain alcohols of the typical “ aromatic ” or ” cyclic ”
series such as benzyl alcohol, or of the closed-chain ” terpene ”
series such as menthol.

PEliFU MEB Y

Belial {Compies Bendv.s, 1919, 168, 945 ; and Boure-Bertrand
Fils, Bulletin, April, 1920, 117), lias dealt witli the isolation of
alcohols in a pure condition after ph^’^sical methods, such as
fractional distillation, have acliiered all that is possible. He refers
to Pasteur’s vrork on the separation of the two alcohols, contained
in the amyl alcohol of fermentation, by means of convertuig them
into sulphuric ethers, acids, and barium salts of different solubffity.
Later, as he points out, the results of the researches of A. Haller
{Coinpies Beudus, 1889, 108, 140 ; 1890, 110, 580) on the borncols
were more general in their scope. They relate to the properties
of dibasic organic acids of acting on alcohols to give acid ethereal
salts soluble m alkalies, and whose solutions when saponified
liberate the original alcohols. The application of this method to
terpene alcohols has been the subject of criticisms by Tiemann and
Eh’iiger {Berichte, 1896, 29, 901). Dodge, in his investigations
of oil of citronella, and numerous other chemists have, however,
utihsed tins method. HaUer has a Iso recommended it for obtaining
pure methyl alcohol bj* preparing the acid phthalate of methjd
bj^ means of phthahc anhydride.

Bouveault has proposed the use of pyruvic acid to identify the
alcohols and separate them from a mixtm’e. He converted the
esters to which they gave rise into semi-carbazones, whence the
alcohols can be regenerated by saponification.

Phenyl isocyanate and diphenyl-carbamyl chloride have since
been used to obtain urethanes.

A. Behai has taken up an old investigation by Liebig and
Wohler, and perfected a method that leads to the formation of
allophai ates together withm'ethanes. It consists in causing cyanic
acid to react on alcohols. The urethanes, however, are generally
only bj- -products of the reaction.

■This method has been apphed to the primary, secondar 3 ^ and
tertiarj' alcohols, wLereas none of the preceding methods were
available for the last named. The author has lilcevise obtained
good results mth terpene alcohols, those of the benzene series,
and lastty with the phenols.

The method emploj^ed for the preparation of these derivatives
is as follows : —

A current of c^-anic acid gas is passed into the cooled alcohol.
The gas is prepared by' the depclj^'merisation of cyanuric acid.
The latter is obtained by’ Behai by causing chlorine to act on urea,
then precipitating the cyanuric acid with ammonia cal copper
sulphate and decomposing the double salt of copper thus formed.

PEBF UMER Y

bj' nitric acid. The cyannric acid is placed in a tube of 12 mm.
internal diameter, wliich is heated to a dark red from front to
back. A current of carbonic acid gas is passed sloudj’- through the
tube, in front of which is arranged a chamber 30 cm. long. The
tube leading the cyanic acid gas into the alcohol has a -wide mouth.
The alcohol rapidly becomes heated, and then suddenly swells up
as a mass of crystals is formed. The crystals, after being cooled,
are pounded in a mortar with absolute ether. The whole is their
filtered and washed udth ether until the ether filtrate no longer
leaves a residue on evaporation. The ether thus removes the
uncombmed alcohol and the urethane, which is always formed to
a greater or less extent.

The insoluble I’esidue consists of the allophanate impregnated
v-ith cyanuric acid. The aUophanate is then dried until the cyanic
odour disappears. It is then dissolved in warm absolute alcohol,
benzene or acetone, from which it cr3fstallises on cooling. The
product is generally pure with the first crystallisation, and°further
crystallisations are needless.

In the case of solid alcohols, the author operates with an ethereal
solution. All the allophanates thus obtained are crystalline,
colourless, and inodorous substances. Thej^ are very slightl}^
soluble in cold ether and are somewhat more soluble in cold
alcohol, though then' solubility is still very slight.

• In the acyclic series the tertiary allophanates are easily
pponified by boiling water. The alcohol is regenerated and urea
is formed with liberation of carbonic acid.

The primary and secondary allophanates are saponified with
gieater difiicultj’’, and in most cases require a boiling aqueous
solution of caustic allcali.

By operating on 5 gi-ams of the alcohol or on a quantity of sub-
stance containing 5 grams, the alcohol may be easily isolated and
identified by the nielting point of its allophanate, the alcohol then
being regenerated in order to determine its physical constants.

Among the terpene alcohols, linalol behaves abnormally, and
Behai suggests that it is not an alcohol, but an oxide.

The cyclic alcohols, with the exception of terpineol, follow the
normal rule.

^ In the arylalkyl series the author has observed some marked
discrepancies in substances containing phenol functions. But if
the phenol function is esterified, the reaction becomes normal.
In the case of phenol compounds in presence of alcohols, it is easj’-
to eliminate the former by treatment vdth alkali.

2—2

P E R F U 21 KEY

ilic alcoliols with an ctlij*lene hydrocarbon function also give
normal alJophanatcs.

Hofmann {ISerjclRc, 1871. 4, 2GS) was the first to give a theory
of the formation of tlie allophanates, and attributed it to the
])rc^ious formation of a urethane, on whieh the cyanic acid
sulxserpicntly acted. Behai is inclined to think that dieyanic acid
ib formed, and that thi.s at the moment of its foi’ination reacts on
the alcohol present. Before the treatment with cyanic acid, he
advise.-^ a fractional distillation, which should be carried as far as
])ossiblc, after preliminary tj-catments with caustic soda and
bisulphite.

The following are the melting points of the alloifiianates of the
imdermentioncd alcohols : —

Alkipl.anntc.

Molt in e:
Point."

Alloplianntc.

jroKiiig

Point.

Hethvl
Elhyi .

Xormal butyl

Isobiityi
Isoamyl
Hexyl .

Isohexyl
Hoptyl
Octyl .

Xonyl .

Hecyl .

Undccyl

Dodecyl
Allyl .

Metliylethylcarbiiiol

212°

Trimctlivlcarbinol

i 190°

190°

Amyl ....

; 152°

119-5° to

Bcnzvl

' 121°

150-5°

riicnylolliyl

180°

1 80-5°

Btljyivauiilvl

173°

150°

Piperonyl

176-5°

105°

102°

Secondary phonvletlivl.

(dccomp.)

181-5°

100° :

Cyclolicxylbutanyl ' .

148°

157° ,

Ginnamyi .

185°

158° i

Cyclopcntaiiyl

• 179-5°

159°

Cyclohexanyl

179°

155-5° to

; i\Icnl]iyl

• 213°

150° 1

Carvomentliyl

; 192-5°

159-5° I

Tertiary mcnlliyl

i 187°

105° ,

, Isopiilegyl . .

! 219°

159-5° j

Plienyl

1 180°

Most^ alcohols form numerous wcll-characteriscd ciystalline
derivatives, which are useful both for identification juirposcs and
for purifying the alcohols.

Amongst these may be mentioned the acid esters of phthalic
acid. (See Comjiics Pewhis, 1SS9, 108. 130S ; 1S96, 1S2 SGo •
Bull Eoc. Chim., 1900, 23, 5-12; Pharm. Zeil., 1899, 44, 258-
Bcnchic, 1910, 43, 1893.) The general method of the formation
of these bodies is as follows : —

Fifty grams of the oil (saponified if necessary) containing the .
free alcoliol (or a fraction of the oil rich in the free alcohol) arc

P E R F U M K R )■

mixed with 50 grams of freshly prepared phthalic anhydride and
25 gi’ams of absolutely dry benzene. The mixture is heated to
110° to 120° for ten hours in a flask under a reflux condenser.
The mixture is cooled, an equal volume of water added, and
caustic soda solution added until the mass is just alkaline to
phenolphthalein. The mixture is extracted several times vith
ether to remove oil not acted upon, and the filtered alkaline liquid
is acidified vitli concentrated hydrochloric acid. The oily phthalate
.‘separates, is washed with water, and dried. To recover the
.alcohols from the acid phthalatcs, the latter are saponified vdth
alcoholic potash, the precipitated potassium phthalate filtered off,
the ethyl alcohol evaporated off, and the rc.sidual insoluble alcohols
arc washed and dried.

The phenjd-urethanes resulting from the reaction of phenyl
isocyanate and the alcohol are also most useful cry.stallinc com-
pounds for identifying the alcohols, as are also the naphthjd-
urethanes. In the preparation of these bodies works on organic
chemistry should be consulted.

For a suggested method of separating primary, secondary, and
tertiary alcohols, see E. Ernrnett Reid, Jow. Amer. Cliom. Soc.,
1917, 1249.

M. D.

ALCOHOLS, DETERMINATION OF, IN ESSENTIAL
OILS. — ^The principles on which such determinations are made
are based on the conversion of the free alcohoLs irrto acetates by
the action of acetic anhydride and the estimation of the esters
formed. When the oil contains both ester-s and free alcohols, the
calculation becomes somewhat complicated, since the alcohols
increase in weight on acetylatiorr, whilst the natrrral esters are
unaffected. It should be pointed' out that, as in the process of
determining the percentage of esters, the results are not strictfy
accm'ate chemical determinations, but are based on the assumption
that the predominating alcohol is the only substance reactirrg with
acetic anlr 3 ’^dride.

The details of the method generally adopted, which should be
strictly adhered to, are as follows : —

Ten cubic centimetres of the oil are gently boiled vdth 20 c.c.
acetic anhj'^dride and 2 grams of fused anhydrous sodium acetate,
in a 100 c:c. round-bottomed flask fitted vith a reflux condenser,
for two hours. The contents of the flask are allowed to cool,
100 c.c. of water added, and the mixture gently warmed on a water
bath to decompose the excess of acetic anhydride. The mixtine

P JC R F i: 21 E PY

ip then transferred to a sci}arator. the aqueous la^'or rejected, and
tJie oil washed with successive quantities of 50 c.c. each of brine
solution containing 1 per cent, of caustic soda and a little idienol-
phthalein until the washings are free from acidity. The oil is then
dried hiy stirring with a little anhydrous sulphate of soda, and
filtered bright through paper.

A suitable quantity of the oil (2 to 6 grains, according to the
proportion of esters present) is weighed out and saponified with
40 c.e.-of semi-normal alcoholic potash solution as described under
the determination of esters. The percentage of total alcohols in
the original oil is then calculated from the following formula : —

IM X N

10(W - 0-042N)

where x is the percentage of total alcohols in the original oil,

X is the number of cubic centimetres of normal alkali used,
W is the weight of acctylated oil taken.

To obtain the percentage of free alcohols, the saponification value
of the original oil must be determined, the saponification value of
the acetylated oil calculated, and the following formula will then
apply

^ r r 1 1 1 (^ — Y]y

Percentage of free alcohols = — rr

° 0-42010(1335-5 — h)

where a = saponification value of the original oil,

b — ,, acetylated oil,

y = molecular weight of the alcohol (monatomic).

In some cases, notably linalol and terpineol, the alcoliol is
partially decomposed b}’’ acetylation in the above described
manner. Boulez {Bvll. Soc. Chim., iv., 1907, i., 117) has recom-
mended diluting 5 grams of oils containing these alcohols with
25 gi’ams of purified tiu’pentine and boiling the mixture with
40 c.c. of acetic anhydride and 3 to 4 grams of anh3!'drous sodium
acetate. A “ blank " experiment to allow for the apparent alcohol
value of the turpentine must, of course, be carried out. (See also
SchimmeVs Re])ori, April, 1907.)

Glicliitch {Bull. Soc. GMm., iv., 1923, 33, 1284, and P. cC:
E. 0. JR., 1923, 401) has proposed a method depending on the use
of a mixtiue of absolute formic acid and acetic anlij^'dride. This
method is based upon Beliaks discovery, in 1900, that the mixed
anhjulride of formic and acetic acids reacts in the cold with
alcohols to give formates exclusively, while phenols remain
unchanged. Behai obtained complex results with linalol oiving

P E P P U M E P

to the fact that he worked at 50° and used an insufficiently low
vacuum for the distillation of the product. It is now shown that
esterification of linalol is complete in seventy-two hours at 20° to
25°, the conversion into geranyl and terpinyl formates being
neghgibly small. The presence of acetic acid, acetic anliydride,
and formic acid in the'acetoformic anhydride does not affect the
results, as these compounds form no addition products vdth
terpenes and sesquiterpenes in the absence of mineral acid.

Preparation of Acetoformic Anhydride. — One part of absolute
formic acid (D 1-22/15°) is added slowlj’’ with constant agitation
to 2 parts of chlorine-free acetic anh^’^ffiL'ide (100 per cent.), the
temperature being kept below 15°. The mLvture is heated during
fifteen minutes to 50° and rapidly cooled. It is kept in a bottle
TOth an emery stopper.

Method of Estimation. — ^Ten cubic centimetres of the alcohol to
be estimated are added to 15 c.c. of acetoformic anliydride in a
30 c.c. flask closed ufith an emery stopper. The mixture is well
shaken, plunged into a bath of ice water (which need not be
renewed), and allowed to remain for seventy-two to ninety-six
hours. It is often possible to esterify in seventy-two hours at
20° to 25°. A greater excess of acetoformic anhydride or a longer
time than ninety-six hours has no effect, good or bad. A smaUer
quantity of the reagent is insufficient for pure linalol. The whole
is then poured into 50 c.c. of cold water, well agitated, and left for
two hom’s without heating. It is then washed successively with
50 c.c. of w’^ater, 50 c.c. of 5 per cent. NaHCOs solution, and
finally twice with 50 c.c. of w^ater. The esterified oil is dried and
saponified as usual, one and a half hours’ hydrolysis bemg given
to ensure the complete saponification of traces of terpinyl
formate.

The alcohol content of the original oil is calculated from the
formula —

n' X M

lQ.{p.n' X 0-028)

where n' — cubic centimetres normal KOH used up,
p — grams of oil taken,

M = molecular w^eight of the alcohol.

Pure Imalol prepared by repeated fractionation of rosewood
oil was used as a test sample. It was soluble in 14 volumes of
50 per cent, alcohol, and had boiling point 63° to 63-5°/2 mm. or
82-3° to 82-6°/ 10 mm., D 0-8630/21°, n 1-4605, and optical rota-

P KB F (■ M FRY

tioii — 17' 30°. The percentage of linalol determined by the above
method was ; —

24 hours’ formylation

Per cent.

78*40

48 „

89*23

,, 3 ,

99*15

00 „

99*31

144 .,

99*31

240

99*15

It has been proposed to determuie citronellol in the presence of
geraniol by means of form 3 ’]ation, instead of by acetjdation, on
the supposition tiiat heating Tiith formic acid decomposes the
geraniol into tcrpencs and similar compounds, the citronellol alone
being esterified.

C. T. Bennett (P, cO E. 0. B., 1921, 351) has exammed this
jDrocess criticalhg and finds it to be unreliable.

The estimation of citronellol bj' heating for one hour on a
water bath with twice its volume of formie acid (100 per cent.)
was finst proposed bj’ Walbaum and >Stephan {BericJiie, 1900, 33,
2,307).

The method was subseciuentl}* used b^y 3Icssrs. SclnmmGl cb Co.
for the estimation of citronellol in otto of rose {ScliimmeVs Reporls,
i^pril, 1901, and October, 1904). The results of several determina-
tions b^’ tliis method were imblishcd in the Perjumcry ami Essential
Oil Record, 1913, p. 32S, and for comparative purposes it was
assumed to be a useful factor. The determination of citronellal
b 3 ’’ the same method has been recommended b 3 ’' Scliimmel tb Co.
(“Volatile Oils,” vol. i., p. 581). Simmons, however (P. cb E. 0. R.,

1913, p. 297), showed that the x^’oeess does not give accurate
results. Kot onl 3 ' does it fail to completch’’ convert geraniol into
terpenes, but it gives high results with jmre citronellol. These
facts were confirmed b 3 '’ subsequent exiDeriments (P. <b E. 0. P.-,

1914, p. 51), when it was shown that a pure citronellol estimating
99'7 per cent. b 3 * acet 3 ''lation indicated 119-S per cent. b 3 ^ the
formic acid method.

In order to further test the method by var 3 dng the conditions,
the following experiments have been conducted in the anal 3 dical
laboratory of Messrs. Wright, La 3 unan and Umney, Ltd. : —

Indicated percentage
' of citroncHoI.

Experiments on pure citronellol.

Heated for one hour on water bath vdth

an equal volume of formic acid . . 99'7

Digested for one hour at 20° C. . . 108*7

P E P F U M E R 1\

Indicated percentage
of citronollol. "

Experiments on j)ure geraniol.

Heated for one hour on water bath . . 46-8

Digested for one hour at 20° 0. . . 82'2

Experiments on equal weights of geraniol and
citroneUol.

Heated for one hour on water bath . . 29’0

Digested for one hour at 20° 0. . . 68*8

Experiments on citronellal.

Heated for one hour on water bath . . 43*8

Heated for tu'o hours on water bath . 33-1

Digested for one hour at 20° C. ... 76-0

Experiments on equal weights of citronellal and
geraniol.

Heated for one hour on water bath . . 29*0

Digested for -one hour at 20° C. . . 68*8

Experiments on Burmese citronella oil.

Heated for one hour on water bath . . 34-6

Heated for two hours on water bath . 30*3

Digested for one hour at 20° C. . . 68*2

Digested for one hour in freezing mixture . 69'2

Citronellal by absorption with 35 per cent.

sodium bisulphite solution ... 52

These results show that the formic acid method is unreliable
for the determination of either citroneUol or citroneUal. These
conclusions are confirmed by A. St. 0. Pfau [Jour. PraJet. Chem.,
1921, 102, pp. 276-282), who finds that the method gives inexact
results, in part because a portion of the geraruol is converted into
the formic ester. With pure citroneUol the author’s results were
irregular and high when 100 per cent, acid was used, and low vdth
a weaker acid. The action of the 100 per cent, acid yields a
mixture of products containing unchanged citroneUol, a smaU
amount of volatUe Uquid which is possibly an aliphatic or cycUc
terpene, citroneUol formate (boiUng point, 99° to 100° at 7 mm.),
the compound C(CH3)20H [CH2]3CH(CH3)CH2CH20CH0 (boiling
point, 129° C. at 5 mm.; specific gravity, 0'9651 ; optical rotation,
1° 46' ; refractive index, 1*4488), and the corresponding diformate
(boiUhg point, 140° to 141° at 7 mm.).

G. T. B.

ALCOHOLS, HIGHER FATTY.— The higher fatty
alcohols are quite analagous to the higher fatty aldehydes {q.v.),
but are so expensive and so unsatisfactory, unless absolutely pure,
that they are not largely employed in perfumery. The alcohols
from 8 to 12 carbon atoms — as they are usually described — have

p ]<: p F u M F n 1

(loraJ odoura of a iiondescripl cliaraclcr, the 3 2 carbon body
recalling the odonr of lily of fhc valley. According to Prins
(P. cb E. 0. P., 1917, G 8 ), octyl alcohol (specific gravity, 0-8278 ;
boibng point. 197*^) lias a useful rose odour. It also recalls
opoponax. Decyl alcohol is useful in iireparing flower odours of
the ro.'=:e typo. Their emjiloyincnt is confined to rounding off
floral odours. An American perfumer has described decyl alcohol
as “ an alcohol which the up-to-date manufacturer uses to deceive
the co]uer of odour.s." (See under the respective alcohols.)

ALCOHOL, ISOPROPYL.— Isopropj-l alcohol or dimethyl
carbinol is now licing employed to some extent in perfumery,
owing to the prohibitive duty on ordinary or ethyl alcohol.
Isopropyl alcohol has the formula CH(OH)(CH 3 ) 2 . When pure
it is a colourless and nearly odourless liquid of specific gravity

0 - 789 at 2 UL and boiling at 82^ to 83°. Its refractive index is

1 - 3749 at 20 '. For perfumery purposes it should be as odourless
as possible, otherwise it is q^iite useless. It is obtained by
numerous reactions, such as that between isopropyl iodide and
lead hydi’oxidc.

It is sold under various fancy names, and various methods for
its preparation industrially have been described. For example,
C. Ellis, of New Jcr.=ey, describes a method depending on the
absorption of the gases from the cracking of petroleum by sul-
phuric acid of specific gravity 1 - 8 . These gases arc very rich in
propylene, which combines with suljfiiuric acid to form an alk}’!
sulphonic acid which is hydrolysed into the corresponding alcohol.
For its comparative harmlcssncss, vida .D. H. Grant, Aniencan
Journal of the Medical Sciences, August, 1923.

ALDEHYDES.— The aldehydes form one of the most impor-
tant groups of the constituents of essential oils, and also of the
more generally employed artificial perfumes. The aldehydes are
characterised by containing a —CO— group which is combined
with one allcyl radical and one hydrogen atom, thus, R' — CO— H,
ethyl aldehyde, for example, being CHg — CO— H. If the — CO —
group is attached to two alkyl radicals, the body is not an aldehj dc,
but a ketone, thus, acetone CH 3 — CO — CH 3 .

Aldchr’des. in general, may be produced by the oxidation of
primary'alcohols {vide Alcohols ”), or by the distillation of the
barium or calcium salt of the corresjjonding fatty acid with
barium formate, thus : —

(R.COO) 2 Ba -4- (H.COO)oBa = 2 BaC 03 + 2 R.CO.H

Bf^rium salt Barium formate Barium carbonate Aldehyde

P E P F U M E P 1’

Tt is often necessary to characterise aldehydes for the purposes
of identifieation. The following arc the most important of their
crystalline comj)oundSj which can be prepared and their melting
j)oints determined for the purpose.

(n) Semicarhazoncs . — Most aldehydes form a crystalline com-
pound with semicarbazide ; the condensation products are knoAvn
as semicarhazoncs. and are u.sually crystalline bodies of sharp
melting point. They are formed according to the following
ci’cation : —

R.COH -i- NHo.NH.CO.NI-L = R.CH : N.NH.CO.NH, ^ H„0

Altlcliyd'j Rcmicnrbazitic Konilcarbazonc

They are obtained by dissolving the aldehyde in alcohol, adding
excess of a mixture in equimolecular proportions of semicarbazide
hydrochloride and acetate of sodium. The mixture is allowed to
.stand for several hours, and water is then added. The precipitated
semicarbazones are recrystallised from methyl alcohol.

ib) Oximes . — ^Nearly all aldehydes form ciystalline oximes by
combination with hydroxjdaminc according to the reaction —

R.COH -L NHoOH = R.CH : KOH -h H„0

Aldehyde Ilydroxylainlne Oxime

Equimolecular quantities of the aldehyde and hydroxylamine
hydrochloride are dissolved in alcohol, and sufiicient alcoholic
solution of potash added to liberate the hydrox 3 'lamine. The
whole is heated on the water bath for sixW minutes.

(c) Phenylhydrazones . — Most aldeh^’des combine with phenjd-
h 3 ’'drazinc to form phenj^Uydrazones, most of which arc crystalline.
Thej’- are formed according to the equation —

R.CHO -f RHo.NH.CcIis = R.CH : N.NH.CJds + HoO

Aldehyde riicjiylhydrarinc Jdicnylhydrarono

Thej' arc prepared by heating the aldehyde in alcohol, under a
reflux condenser, with phenjdhydrazine hydrochloride and sodium
acetate for an hour.

Other compounds will be referred to where necessaiy under
particular aldehydes. {Vide “ Aldehj’des, Determination of,” and
“ Aldelydes, Higher Fatty.”)

ALDEHYDES, DETERMINATION OF.— The determina-
tion of aldehydes is one of the operations which the analyst has
to undertake most frequent^ to decide upon the value of ra^v
materials for the perfumer. In such oils as lemongrass, cassia,
cinnamon, and lemon the estimation of the aldehydes is the
determining factor as to the value of the oil.

The most general process in use amongst analj’-sts depends on

P E P F U M EP y

the fact that most aldehydes possess the power of forming com-
jDOunds %nth sodium bisulphite or sodium sulphite wliich are
soluble in water. In general, the processes used for the determina-
tion of aldehydes depending upon this fact are equall}^ applicable
to the determination of ketones. The following processes are of
general appheation to most of the aldehydes and ketones : —

{a) Bisul'phite, of Sodium Process. — ^Five cubic centimetres of
the oil in which the aldehj’-des are to be determined are placed in
a flask holding alrout 150 to 200 c.c., with a long neck which is
graduated in c.c. To this is added 50 c.c. of a hot 30 jDer cent,
solution of sodium bisulphite, and the whole well shaken. The
flask is placed in a boiling water bath and is repeatedly shaken,
with the gradual addition of more bisulphite solution, until all
crj'stals formed have disappeared and a clear oily liquid rises to
the surface. The shaking should be repeated and vigorous, and
the process should last from an hour (lemongrass oil) to two hours
(cassia oil). More bisulphite solution should be poured in, up to
nearly the top of the neck, and the flask stood aside for twenty-four
hours to allow the whole of the rmabsorbed portion to rise into the
graduated neck. As the specific gravity of both the absorbed and,
unabsorbed constituents do not differ greatly, the calculation by
volume is m juactice accepted as accurate. So that if 4 c.c. have
been absorbed by the bisulphite and 1 c.c. rises into the neck of
the flask, the oil is returned as containing 80 per cent, of aldehydes.

(&) Neutral SuIjFPte Process. — The determination is carried out
exactly as in the case of the bisidphite process, except that the
absorbing solution is one of neutral sodium sulphite and the end
of the process is controlled by a definite reaction; A few drops of
phenolj)hthalein solution in alcohol are added to the contents of
the flask, and a red colour is soon developed in the flask due to
the liberation of free aUcali during the process. A few drops of a
10 per cent, solution of acetic acid are added till the colour
disappears, and the shaldng repeated. This is done so long as the
red colour develops, and when no return of the colour occius after
ten minutes the absorption is complete, and the result is read off
in the neck of the flask after twenty-four hours.

(c) Hydroxylamine Method . — ^The fact that aldehydes form com-
pounds with hydroxjdamine was first utilised by Walther [Pharm.
Central., 1899, 40, 621) for the quantitative determination of this
group of bodies. The original process, shghtty modified by A. H.
Bennett, is practically universally used for the determination of
citral in lemon oil and similar oils wfliere only small quantities of

PEBFV MEB Y

aldehydes are present. Twenty cubic centimetres of the oil are
mixed with 20 c.c, of seroinormal hydroxylamine hj’^drochloride
solution (in 80 per cent, alcohol), and 8 c.c. of normal alcoholic
potash solution and 20 c.c. of 90 per cent, alcohol are added.
The mixture is gently boiled for thirty to forty-five minutes under
a reflux condenser, and then allowed to cool. The condenser is
washed down with water, and the contents of the flask brought
up "to about 250 c.c. with water. A blank experiment is carried
out vdthout the oil. A few drops of phenolphthalein are added
and the mixture neutralised to tliis indicator 'with alcoholic potash
solution. Methyl orange is then added and the mixture exactly
neutralised to this indicator vith seminormal sulphuric acid.
The end reaction is not easy to determine, so that the method of
spotting on a white tile vdth drops of the indicator is resorted to.
Each cubic centimetre of seminormal acid is equivalent to
0-076 gram of citral (or the equivalent quantity of any other
aldehyde), so that 20 c.c. of the oil (calculated to weight by
multiplying by the specific gravity) contains 0-076 x a; grams of
citral, where x is the number of cubic centimetres of seminormal
acid consumed.

Eurther methods of special application will be found under

Citral. (Vide also E. J, Parry, Chemistry of Essential Oils,
etc,, vol. ii., Scott, Greenwood & Co., London ; and Bennett and
Bateman, P. c6 E. 0. P., 1923, 268.)

ALDEHYDES, HIGHER FATTY. — ^During the past few
years a most -valuable addition to the perfumer’s art has been
made by the manufact'ure on a commercial scale of the higher
aldehydes of the so-called fatty series. As a group these bodies
possess an extraordinarily powerful odour, of a fruity nature, which
is so po'^verful and persistent that a single drop spilt on one’s
clothes renders one sufl&ciently odoriferous to be objectionable.
They must be used with great discretion and in minute quantities,
as otherwise the great improvement effected in a floral odour by
them use tends to pass to an objectionable and penetrating strength
which spoils the whole bouquet. Properly blended and used with
discretion, they are of the highest value to a perfumer wdio wishes
to ‘‘create” his own proprietary bouquets. They are^equaUy
of value m the rounding off of fruit essences. The following are
the^ principal of these peculiar aldehydes, which, on account of
their proneness to oxidise, are frequently* sold, in 10 per cent,
alcoholic dilutions, which are very convenient for use in measuring
out very minute quantities.

p E n F u M E Ji y

Ileplylic Aldehyde, CH 3 (CH 2 ) 3 .CHO. — Tliis body is also known
as oenanth^dic aldcln’dc, and is prepared by llic dry distillation
of castor oil under a pressure of 100 mm. Only small quantities
can bo dealt with at a time. It may also be prepared by “ esteri-
fying ” castor oil by methyl alcohol j using hydrochloric acid as
the condensing agent and distilling in vcicno. When the tempera-
ture rises to 250^ at 12 mm., no more is distilled, as the residue is
more or less unaltered castor oil. The aldehyde is accompanied
l)y metlqvl undccylenate. and can be separated by means of its
bisulphite compound. It is an oil of strong fruity odour, boiling
at about lo2'’. and having a specific gravity 0-S20 and I’cfractivc
index 1-4150.

Ociylic Aldehyde, CH3(CH2)c^'^^0- — eight cai’bon
aldehyde, and is found naturally in ncroli and rose oils. It is
of considerable value in perfumes of the rose, jasmin, geranium,
neroli and orange types. The starling point of this bodj^ is
cocoa-nut fat. The fat is saponified, an<l the fatty acids separated
1)3' the addition of dilute sulphuric acid. The aqueous liquid is
extracted with petroleum ether, to obtain the fatty acids soluble
in water, and these are added to the previously* separated fatW
acids. The principal fatty acids ])rc.sent are caprylic and lauric
acids. These arc jiow washed with a little water, dried over
anhydrous sodium rsulphatc. and heated under a rcfiux condense)’
for six to cicht hours with their own weight of methyl alcohol and
a small amount of sulphuric acid. Water is then added, and the
oil sej)arating is washed with water and then with dilute alkali.
The esters so formed are then fractionated in vacuo, the earlier
runnings containing most of the methyl caprydate, whilst the later
runnings contain the methyl laurate.

The methyl caprylatc is reduced by sodium and alcohol, and
yields octyf alcohol CH3(CH2 )c.ChJ 0H. This body is then
converted by a controlled oxidation into octylic aldehyde. It is
a liquid of powerful fruity odour, having a si)ecific gravity 0-S27,
refractive index T4105, and boiling point 82° at 13 mm., or 175°
at 7 GO mm.

Nonylic Aldehyde, CH 3 {CH„) 7 .CHO, is the nine carbon aldehyde
of the series, and occurs naturally' in both rose and orange oils.
It is used in the same manner as octylic aldcliyvle. It is an oil of
specific gravity' 0-S277, refractive index 1*4245, and boiling
point 92° at 13 mm. Its melting point is from + 5° to -}- 7°.
It is prepared as follows : Undecydcnic acid, one of the products
of the dry distillation of castor oil, is carefully melted with caustic

PERFUMER r

potash and water until no more hydrogen is given off. The mass
is exhausted with water, and dilute sulphuric acid is added to the
aqueous extract. This precipitates pelargonic acid, which is
esterified ndth ethyl alcohol in the usual manner. The ethyl ester
is reduced by sodium and alcohol to nonylic alcohol, which, by
controlled oxidation, jdelds non 3 dic aldehyde. {Vide also Levdn-
sohn, P. t& E. 0. R., 1924, 12.)

P. Bagard [Bull. Soc. Chirti. (4), 1, 346) has prepared nonj^lic
aldehj'de b}’" the dry distillation of a-hydroxycapric acid, which
he obtains b}’’ starting from pelargonic acid and passing tlmough
the intermediate stage of capric acid by means of the reactions —

^CHg— (CHa),— COOCoHs

CH3— (CHo)-— COOH-

Pelargonic add

-^CH3—(CH„),-CH20H-»CH3-(CH2),-CH3Br
->CH3— {CHa)^— CH3— CISWCH3— (CH2)7— CHa— COOH

_ Cajiric acid

(CHa)7— CHBr— COOH

->CH3— (CHa) 7— CHOH— COOH

a-IIydroxycapric acid

The same author has obtained decjdic aldehj^de b}'- the distilla-
tion of a-hj^droxjmndecjdic acid prepared from undecylic acid,
which is itself obtained from undecjdenic acid.

The characteristic derivatives of these aldehydes described by
Bagard (for their preparation, see the original paper) are ; the
semicarbazone of nonylic aldehyde, melting point 100° C. ; the
oxime of nonjdic aldehyde, melting point 64° C. ; the oxime of
decylic aldehyde, melting pomt 69° C. : the azine of decylic
aldehyde, melting point 34° 0. {Roiire-Berlrand Fih, Bulletin
Maj’-, 190S, 44.)

Decijlic Aldehyde; CH 3 (CH 2 ) 8 .CHO, or the ten carbon aldehyde
of the series, is prepared in the same manner as nonyHe aldehyde,
starting from capric acid instead of pelargonic acid. It is most
useful in the. reproduction of the odours of violet, orris, neroli,
cassie flowers, rose and orange. It is probably the most general^
used of the series so far as perfumers are concerned. It is an oil,
boiling at about 212°, of specific gravity about 0-828 to 0-834,
and refractive index 1-4298. (See above, under “ Nonvlic
Aldehj^de.”)

Undecylic Aldehyde, CH 3 (CH 2 ) 9 CIIO, is the eleven carbon
aldehyde of the series. This aldehyde is made from the method
ester prepared from the crude lamic acid of cocoanut fat, as
described under Octylic Aldehyde ” above. The methyl lam-ate
is saponified in the usual manner, and the resulting lauric acid is

31 .

p }<: li F V M p: li y

degraded according to tlic method of Blaise. It is treated with
PCI 5 , wliich transforms it into lanryl chloride, which is brominated
and the rcsnlting compound hydrolysed to bromo-laurie acid.
This is convej’tcd into oxylauric acid Ijv means of caTistic alkali.
Oxylanric acid is directly converted into undecylic aldehyde by
heat. This aldehyde, which has an intense floral and fiaiity odour,
boils at 117' to 118^ at 18 mm. It has a specific gravity 0*825 at
23'. a 7 id I’cfractive index 1--1320.

AJdcJii/dc, CII;,(CT]n)]oC'nO, or laui'inic aldehyde, was

riginally recommended for blending with violet ])erfumes, but is
not well adapted to this ])urpose. Jt results from the reduction
of ethyl lauratc by sodium and alcohol, and controls oxidation
of the resulting alcohol. It is a solid ])ody, melting at 44° to 45 °,
boiling at 185° at 100 mm., and rajudly oxidising to lauric acid.
It should therefore be ke])t in alcoholic solution.

Tndcnjl AhPlnjdc, CH..(CTTo)jjCIIO. — This aldehyde has no
distinctive flower perfume, but is exceedingly powerful, and can
be used in most floral perfumes. American perfumers state that
it has licen used with great .success by those wishing to ei’oate
special bouquets.

Tctradccvl and hexadccvl aldehvdes. containing 14 and IG
atoms of carbon rc.spcctively, have intense odours, the former
recalling peach, and the latter strawbcriy. Psed in extremely
minute quantities they arc of great value to the perfumer, but
if the quantity exceeds mere traces the composition is ruined.

Ilcxjilcnk Aldehyde., CH.vCIL.CHo.CK : CIl.CHO. i,s an un-
saturated aldchvdc of the fat tv scries. It has an odour recalling
those of vine and strawbeny leaves.

(Refer to Wcyl. *' IMethodcs dc chcmic organique ; aiid to
Ullmann, “ Enzyklopcdie d. tech, chemie,” voi. 0.)

A* VJr*

ALECTORIA. — This i.s one of the lichens growing on oak and
other trees from which the extract known as mousse dc chenc or
oak moss is manufactured. The perfume obtained is not so fine
as that from other lichens such as Fvernia .'species.

ALLSPICE. — ^Allspice or pimento consists of the ' dried
unripe fruits of Eugenia ■pimcnla [Pimenfa officinalis, Lindlcy), a
plant belonging to the natural order Myriacecc. The sxncc takes
its name from its resemblance in perfume and flavour to a mixture
of cinnamon, cloves, and nutmeg. It is sometimes known as
Jamaica pepper.

The plant is a native of the West Indies, found on calcareous

PERFUMER Y

soils near the coast in Cuba, Hayti, Trinidad, Domingo, and
various islands of the Caribbean Sea. The chief part of the
world’s supply, however, comes from Jamaica, Mexico, Costa
Rica, and Venezuela also produce some of the spice. The fruit,
after gathering, is carried in baskets to the barbecue, a paved
court divided into compartments by a low sill so that the berries
of different days’ gathering may be kept separate. They are
spread out in the sim and turned over with a wooden rake so as
to expose them thoroughly to the sun. They take from three to
twelve days to drj^, and must be well protected from damp,
which damages them materially. The average annual output
from Jamaica is about 11,000,000 lb. [Vide Ridley, "Spices,”
Macmillan & Co., London.)

The berries yield from 3 to 4-5 per cent, of essential oil on
distillation, wliich contains a large proportion of eugenol. It has
the following characters : specific gravity, 1-024 to 1-056 ; optical
rotation, —0° 40' to — 5° ; refractive index, 1-5250 to 1-5350 ;
and eugenol value, 65 to 80 per cent. It is soluble in twice its
volume of 70 per cent, alcohol, with, at most, slight turbidity.

The oil distilled from the pimento leaves is also rich in eugenol.
Experiments on a considerable scale are being carried out by the
Department of Agriculture of Jamaica with a view to marketing
the oil for the extraction of its eugenol for vanillin manufacture.
The leaves jneld from 0-4 to 1-2 per cent, of oil, usually containing
from 85 to 92 per cent, of eugenol, although the leaves from the
Walderston district often 3 neld oils of much lower eugenol value.
The departmental chemist, Mr. E. E. A. Campbell, considers that
distillation by means of dry steam under pressure is the best
method to be adopted, and he does not consider that the addition
of salt to the water in the stills is of any special value.

ALLYL - PULEGON E. — ^Haller and Ramart [Gomptes
Rendus, 1924, 179, 120) have prepared a number of allcyl-pulegones
from the pulegone obtained from American pennyro 3 ’’al oil. They
describe it as having an odour resembling those of ionone and
oil of vetivert, and consider that it may have a commercial
value.

ALLYL SALICYLATE.— This compound, CHg.CH.-CH.OOG
(OH).C 6 ll 4 , is prepared by heating under a refiux condenser a
mixture of equal parts of sahcylic acid and aUyl alcohol with a
little sulphuric acid. It is a liquid of floral and fruity odom-,
boiling at 247°. It is not used much in perfumery, but has been
r- 33 3

PEBFV MEET ■

rcconiinenclGd for modifying flower odours {Bgv. GJicm. Ind.^ 1911,
p. 129).

ALMONDS, OIL OF. — ^An essential oil is obtained from tlie
kernel of the bitter almond, Pnmvs amygdahis, which is identical
with that obtained from either j^each or apricot Imrncls. Tlic.5C
oils are so nearly identical that for all practical purposes they aie
interchangcahlc.

Bitter almond oil docs not exist as such in the kernels, hiit
results from the action of water on a glucosidc, amygdalin, uhich is
present, under the influence of the ferment, cmulsin, which is also
present. In commerce the fixed oil is expressed, and the press
cakes are ground up and soaked for twenty-four hours in water
usually containing some salt. The essential oil is by this time
fully developed, and is then distilled. The glucosidc on decompo-
sition yields dexti-ose, henzaldchyde, and hydrocyanic acid. The
essential oil consists almost entirely of henzaldchyde, with se\eial
per cent, of the highly poisonous hydrocyanic acid. Fiiis is
removed in various ways ; for example, by mixing the oil with
water, red oxide of mercury, slaked lime, and feiious chloiidc,
out of contact with the air, and heating it on a water hath. The
hydrocvanic acid is decomposed, and the rectified oil now consists
of nearly pure henzaldchyde.

As hydrocj’anic acid is a very deadly poison, it is of the liighest
importance to see that it is free from any traces of the acid. Such
oil is sold as “ S.A.P." {sh\e acid. 2 '>rvssic.). In order to test for this,
a few' drops are dissolved in alcohol and a few drops of solutions
of ferric chloride and ferrous sulphate arc added. A slight excess
of caustic soda solution is then added, and the precipitate formed
is dissolved in pure hj'drochloric acid. A deep blue coloui oi
precipitate (prnssian blue) appears if traces of hydrocyanic
(prussic) acid arc present.

A pure hitter almond oil free from prussic acid has a specific
gravity 1-049 to 1-055, refractive index 1-5420 to 1-54G0, and
boiling point 179°.

The oil requires careful preservation away from air and light,
especially if it contains traces of w’ater. It is liable to oxidise -
rapidly if not so preserved, with the formation of benzoic acid.

This is determined by titration w'ith ^ caustic allcali, and should

not, in good sanijiles, exceed .1 per cent.

The old adulteration of almond oil with nitrobenzene is now
quite apocrjqihal, the onfy adulterant used in actual practice

■PERFUMERY

being artificial benzaldehyde [q.v.). If the latter body contains
more than the merest trace of chlorine -(which is introduced during
the process of manufacture), it is not suitable for perfumery
purposes, since it tends to darken any pale substance, such as
white soap, which it has been added to. But if the artificial
benzaldeh 3 ’-de be absolutelj’- pure, it forms an excellent substitute
for the natui’al oil, at a veiy much lower price.

It is usual to saj’- that the natural oil is a trifle more delicate in
odour, but this is veiy doubtful, and as a largo proportion of the
oil sold as natural is, in fact, ahnost, if not quite, entu’cly artificial,
the perfumer is recommended to paj'- attention to the artificial
benzaldelyde or to purchase the natural oil from recognised actual
distillers of reimte. {Vide " Benzaldelyde.”)

ALOE WOOD.— FuZe “ Linaloe oil.”

ALOYSIA CITRIODORA.— FZfZe “ Verbena Oil.”

ALPINIA OILS. — ^The fresh roots of Alpinia Malaccensis
yield about 0-25 per cent, of essential oH containing methyl
cinnamate. It has a specific gravity 1‘039 to 1'047 at 27° ;
optical rotation, -j- 0° 15' to 1° 30' ; refractive index, 1*5477 ;
and saponification value, 256 to 278*5. The leaves, accorduig to
van Romburgh {Ko7i. Alcad. Weten. Amsierda7n, 1898, 550), yield
0*16 per cent, of essential oil containing pinene, and 75 per cent,
of metlyl cinnamate. Its specific gravity is 1*020 at 26°, and
optical rotation + 6° 5'. Ultee {Amialen, 1914, 405, 175)

exammed the oil from Alpinia Galanga and found it to contain
50 per cent, of methyl cinnamate and 20 to 30 per cent, of cineol.
The oil had a specific gravity 0*974 to 0*985 ; optical rotation,
+ 4° to -{- G° ; and refractive index, 1*5164. Gardies {La Par-
fumerie Moderne, 1923, 109) has reported on an oil from Tonlcin,
known as Beio-Rieng, which possesses a fine odour of an infusion
of tea. It is possibty an Alpmia oil. It has a specific gravity
0;902 ; optical rotation, +8° 8' ; refractive index, 1*4884 ;
esters, 3-8 per cent. ; and free alcohols, 33*8 per cent.

AMBER, ARTIFICIAL. — The so-called artificial ambers
or “ ambres ” are merely mixtures of heavy odour-bearing
substances together with (usually) animal fixatives. For example,
musk, civet, castor, mousse de chene, balsams of Peru and Tolu,
storax and cinnamic esters enter into their composition. The
odour is generally far more pronounced than that of ambergris.
A nitrated dibromo-butyl-?n-cresol methyl ether, melting at about
100°, has been suggested as an artificial amber.

36 3 _.

PERFUMERY

AMBERGRIS. — ^Ambergris is an exceedingly valuable raw
material of perfumery, as are several other animal products ; it
is also very expensive. It is an opaque grey, yellowish, or black
material, occurring in lumps of all sizes, the largest piece yet
recorded being one weigliing about 200 lb. It is found on the
sea coast or floating on the sea near the coasts of India, Afiica,
and Brazil. About thirty years ago a large proportion of the
ambergris sold on the London market was collected by the whalers
of Tasmania and New Zealand who phed their trade in the
Antarctic Ocean. The industry has now ceased to exist so far as
Tasmania is concerned, but the New Zealand flshermen occasion-
ally bring in some ambergris. As this substance has been
surrounded by mystery for many years, it will be of interest t;o
briefly note the following views which early writers have expressed
as to the actual origin of ambergris. An early writer, named
IQobius (“ Perfumery ” (E. J. Parry), Sir Isaac Pitman & Sons,
Ltd., p. 73), gives, amongst others, the following views which have
been entertained as to its origui ; —

(1) It was beheved to be the excrement of a bird, eommon in
Madagascar, melted by the sun’s heat, washed out to sea,
swallowed by a whale, and passed through its body unaltered.
(2) Others believed it to be excrementary material of certain
cetaceous animals. (3) It was siumised to be a wax or gum
exuding from certain trees growing on the sea shore, which dropped
into the sea, congealed, and so became ambergris. (4) A common
idea m the Orient was that it sprang from the bed of the sea as
naphtha does from the earth, or that it was a kind of bitumen
gradually working up from the ocean and hardening in the sun.
(5) By some it was held to be a kind of marine fungus torn up
. from the bottom of the sea by violent tempests. (6) The origin
of ambergris was also ascribed to honeycombs which had fallen
into the sea from rocks where bees had built then nests. (7) Dr.
Boylston and Mr. Dudley [PMl. Trans., 385, 387) asserted that
ambergris was an animal concretion found in balls in the body of
the male sperm whale. (S) A certain Herr Neumann, chemist to
the King of Prussia {Phil. Trans., 433, 434, 435), denied that
ambergris was an animal product at aU, and that, if it were found
in whales, it must have been first swallowed by them. His own
opinion was that it was a species of bitumen exuding from the
earth hito the sea. An old scientific v,^ork of the eighteenth
century states ; “ The pieces are frequently seen composed of
divers strata . . . with stones and other bodies enclosed within.

r E M U M E K X

and tlie strata are sometimes full of little shells . . . whence it
maj'- he conjectm’ed that the ambergris had originally been in a
fluid state . . . and enveloped such bodies as happened to he in
its way.”

Ambergris is now definitely known to be a pathological secretion
of the sperm whale PJiyseier macrocepliahis. Sometimes the whale
manages to reject the secreted ambergris, and then recovers from
his disease ; otherwise he dies. As a rule, the dead body is eaten
hj’ fish and the ambergris liberated, when it may be found floating
on the water or may he washed ashore. If a sick whale is caught
ahve, the whalers may make more out of the ambergris than out
of the whole carcase.

Jean Gattefosse, in' an article on ambergris {La Parfmnerie
Moderne, 1920, 259), gives the following as the method by which
ambergris is secreted by the sperm whale. The odorous con-
stituents of ambergris, in his opinion, exist already formed in
certain cejihalopods such as Elodone moschata, upon which the
whale prej'-s to a very considerable extent. In normal circum-
stances these substances, as well as the crystalline ambrein, are
expelled in the fceces. But if the whale be sufiering from a certain
micro-organic intestinal disease, these bodies are not expelled.
The lumps of ambergris are then formed by the crystallisation of
the ambrein with other matter, as those substances not concerned
in the formation of the calculi are consumed by the bacteria. The
lumps are then expelled fortuitously or, if not, result in the
animal’s death.

According to V. Hasslauer {La Parfimerie Moderne, 1921, 56),
ambergris is a calculus formed in tire sperm whale by the un-
digested residues of its food, combined vdth biliary and gastric
juices, blood, and sometimes faecal matter. The calculus, when
found in the interior of the animal, is not of the same quahty as
that which is expelled. The sperm whale is very migratory, going
far afield in search of his food. It furnishes ambergris varjdrrg in
character according to where it is caught, thus indicating that
the natine of the food influences the character of the ambergris.
Hasslarrer claims that it is possible, from the odour and aspect of
the ambergris, for an expert to say from what part of the world it
comes. Ambergiis which has been expelled and exposed to the
sun for several years is certainty of the finest quality.

Some excellent work on the formation of ambergris was com-
menced by Bauregard (“ Les cr 3 'ptogames de I’ambre gris,” Ann.
de mierograpMe de Miqnel, 1898). He separated an organism,

PET^FV MERY

whicli he caUcd Sjnrilhts racli PhjsGieris, from the intestines 'of
the animal -which appeal’s to he responsible for slowly attacking
the faecal matter and thus contributing to the formation of the
calculus. His regretted death stopped this very promising
investigation.

The value of ambergris in perfumery lies in its very high fixative
jDOwer, coupled with a slight animal odour, which has always been
an attraction in the most refined perfumes so long as it is not too
highly accentuated. In common with other animal perfumes, it
has m some quarters held a reputation as an aphrodisiac, but this
is quite without foundation.

It occurs in characteristic lumps of grey to greyish-yeUow or
black coloiu’, vith a characteristic odoiu’ and a somewhat greasy
surface. It has a specific gravity of about 0*900 to 0*920 and
softens at about 30°, melting at about 40°.

The exact composition of ambergris is not known. Pelletier and
Caventou (“ Traite de chemie,” 1805) claimed to have isolated a
substance which they term ambrein from it, and Chevalier, in
1828, again separated it. In 1912 Eiban found that tliis was a
mixture, but by repeated recrystallisations he isolated a pure bodjq
for which he retained the name ambrein, and which melts at 82°.
Traces of aromatic acids and of an essential oil arc also present.
The actual odour bearer has not yet been definitel}'- characterised.

Ambergris is used in perfumer}’- m the form of an infusion in
90 per cent, alcohol, usuaUj’- of about 5 per cent, strength. It is
usual to macerate with regular shaking for a period of from-one to
three months.

Artificial ambergris and similar preparations have no relation-
ship vdth the natural substance, but are merely ‘‘ imitation ”
ambergris, having an entirely different odom’, but which are
useful as fixers and contribute to the “ hea-vy ” type of odour.

The P. cfc E. 0. R, (1922, 300) gives the follovdng details of
the examination of true and false ambergris by H. I. Cole, of
the Bureau of Science, klanila : —

In 1912 Riban [Com^ites Rendus, 1912, 154, 1729-1732; Bull.
Soc. Cliem., 1912, iv., 11, 754-757) investigated ambrein more
closely. He had come into possession of a small quantity of
ambrem wliich had, in the course of time, separated out from the
alcoholic fiquid in a bottle contamuig extract of ambergris. The
substance, after being recrystalhsed from alcohol, melted at
between 82° and 86° C. It is a wMte crystalline sohd separating
from its alcoholic solution in slender needles. Combustion showed

PERFU MERl

it' to^ possess the formula CagH^oO. The compound tends to
remain in the superfused state when melted, even if sown with
crystals. When warm and dry, it becomes highly electrified on
slight rubbing. It is not optically active, has a neutral reaction,
and is insoluble in water, but soluble in most organic solvents.
When acted oh by bromine in carbon tetracliloride solution, it
gives an octo-bromo derivative OogHgoOBrs, a white vitreous
solid. ^ Chlonne, under similar conditions, decomposes it. On
warming ambrein with phosphorus pentachloride, a wliite amor-
phous mass of pentachloro ambrein CggHggClgO is obtained.

The physical constants of ambergris as given in literature
vary widely. No chemical methods for its identification are to
be found, m the literatme available; The Chinese test its purity

by scraping it upon boiling tea, in which they consider it should
dissolve.

A number of substances suspected of being ambergris have
been submitted to the Bureau of Science for identification, but one
in particular is so generally considered to be the genuine article as
to deserve the name “ supposed ambergris.” This substance is
usually found floating far out at sea in localities known to have
gelded ambergris; It is picked up by fishermen and sold to the
Chinese and Moros as ambergris. It has been shipped through
the Custom House of Manila to Japan, rated as “ ambergris,” and
IS used by the natives for medicinal purposes, and by the Chinese
and Moros probably as an aphrodisiac. In aU physical appear-
ances It closely resembles ambergris. It occurs in the same places,
IS found in the same quantities, and has approximately the same
specific gravity, and a similar mottled appearance. It, however,
has a slightly different odour, and becomes brittle on agehn^ while
true ambergris apparently does not. Since no methods of° identi-
fymg it positively as ambergris were available, the matter was
referred to the Bureau of Chemistry at Wasliington. That bureau
reported that ” there are no satisfactory methods by which it is
possible to identify ambergris. Perfumers are in a better position
to determme the genuineness of this material than we would be by
ordmary analytical methods.”

It seems therefore that ambergris is determined in a manner
analogous to that of a good wine ; that is, it is judged by a
connoisseur, one who recognises it by general appearance, boquet
or odour, etc., from a physical rather than from a chemical or
microscopical standpoint.

Samples of the substances were sent to the leading perfumers of

PERFUMERY

PEBFUMERl

PERFUMERY

the United States and Europe "uith the request that an opinion be
rendered as to 'whether the material was true ambergris. The
rephes were almost unanimous against the substance being
ambergris. At this point the facts were brought to the attention
of Mr. Cole. It seems that ambergris often contains “ the horny
giUs of a cuttlefish species ” (Bruff, Cliem. Ahstr., 1916, 10, 1405)
which serves as food for the whale. A careful microscopical
exammation proved the absence of such horny material, but led
to the finding of occluded fragments of moss, leaves, and bark,
so distributed as to suggest inclusion in the formation of the
substance rather than foreign material gathered up after the
lumps were formed. This naturally indicated a vegetable rather
than an animal origin'. A comparison ■^dth the samples of gums
and resms at the Bureau of Forestrj' showed the substance to
have a close ph 3 'sical resemblance to the latex from Ariocarpus
elasiica (“ Philippine Resins, Gums, and Essential Oils,” Ball.
P. 1 . Bvr. .Forestry, 1920, 20, 68. Some of the ph^’^sical and
chemical constants of this latex, and of the “ supposed ambergris,”
v'ere determined. The results are fisted in the table on p. 40.
The known constants of true ambergris are given for comparison.

From the data given above and the microscopical examination
we are led to the conclusion that the various samples of “ supposed
ambergris ” submitted to the Bureau of Science were neither
ambergris nor of anunal origin, but that they were originally
derived from a tree, probably closety related to Artocarpus elasiica.

Recently a substance which had been found in southern
Palawan, near Balabac, by a Moro was submitted to the Bineau
of Science for analj^sis. It proved to be true ambergris. (This lot
of ambergris weighed 47 kg.) The material was of a waxy nature,
bro-wn, -ufith tiny specks of white distributed through it, and there
were also embedded in it many fragments of the chitinous part of
the internal shell or gladius of a cuttlefish. Other cliitinous frag-
ments, in the form of a parrot’s beak and the remains- of the
mandibles of the cuttlefish, were also found. This chitinous
material is identical with the “ horn}'' gills of a cuttlefish species ”
referred to above. These fragments appear as thin dark brown,
opaque, finel}- striated pieces of eliitin varying in thickness from
0-04 to OT mm. No moss, bark, or other vegetable material was
found in the sample.

The specific gra-Mt}’- of the ambergris was 0-834 (? 0-934). The
melting point was 65° C. The ash content was 0-21 per cent.
After the ambergris was melted it remained as a brownish-black

PERFUMERY

viscous mass on cooling. Attempts to crystallise the ambrein
from alcohol v^ere unsuccessful. No cr^^stallisable product could
be obtained upon acetylisation with acetic anhydride.

The above data, and especially the microscopical examination,
proved that this substance was ambergris.

]Mr. Cole emphasises as his conclusion that a careful micro-
scopical examination of substances suspected of bemg ambergris
will often prove to be of greater value in the identification of
such substances than the ordinary pliysical or chemical methods.

AMBRETTE, OIL OF* — ^Ambrette seeds, or the seeds of
Sibtscus A-bshuoscJiU'S, also knoAvn as musk seed, is a valued
aiticle in perfumery. The name Hibiscus is possibly derived from
Ibis, the stork, a bhd which is said to chew the plant. The name
Abclmoschus is derived from tlie Arabic kahb-el-misk grain of
musk The plant is herbaceous, growing to about 6 to 8 feet
in height, a native of the hottest parts of India. It belongs to the
natural order Malvacc(B, Its large yellow flowers yield small grey
seeds vdth a pronounced odour of musk, Avhich are distilled for
then’ essential oil. The latter is a highly aromatic liquid, of
specific gravity 0*900 to 0*905, semi-solid at ordinary temperatures,
the melting point varjdng with the quantity of free fatty acids
wliich it contains. Samples of pui’e oil are sometimes quite fluid,
qvdng to comparative freedom from palmitic acid. Farnesol has
been identified as a constituent of the oil. Schimmel S Co.
{Report, April, 1912, 23) distinguish between the normal oil and
the oil depi'ived of its fatty acids, which is liquid at ordinary
temperatures. They give the following figures for the two oils : —

ITormal oil.

Liquid oil.

Specific gravity at 15° '

0-9088 to 0-9123

» „ 40°

0-891 to 0-892

,, ,

Optical rotation

+0° 14' to 4-1° 19'

Refractive index at 20°

1-47421 to 1-47646

Acid value

75 to 132

0 to 2-4

Ester value

66 to 113

167-7 to 180-5

Solidif3nng point

38° to 39°

iSolubiiity . . .

Insoluble in

Soluble in 3 to 6

10 vols. of

vols. of 80 per

' -

90 per cent.

cent, alcohol.

alcohol.

P E R F U 31 E R ]

Lalouo and Littcrcr [Roura-Bi.rtraml Flh, Bulletin, October,
1912, IS-j) obtained the following rtgnr('‘4 for a normal oil ; —

Bj)eciric gravil y at

?Af

.}:r

0-S9S9

0-SRS3

Optical rotation , . . , . -]“1° 2-1'

Itefractive index at 90° .... l-4G-j5

Soluble' in 1 volume of 90 ])er cent, alcohol, but
a .stremg tur])idify is ju’oduced on the subse-
quent addition of the same' alcohol.

Acid value . . . . . .47-0

Saponification value ..... I9;v3

,, ,, of the acelylatcd oil . 2]3‘7

ARIiMONIA. — So ’Called lirpiid ammonia, and ammonium
carbonate arc employed to a considerable extent in tlic manu-
facture of ])erfumed .smelling salts. “ Li<juid ammonia is a
solution of gaseous ammonia. Xlb.. in water, with wliich it forms a
liydrate XIl;.Oir. 'rhe stronge.-l solution of commerce has a
specific gravity (t-880, and contains ho'G ])er cent, of KIL ])y
weiglit. The following table gives the strength of solutions of
ammonia of various specific gravities ; —

S| ecific
Liiavit V
liV ^

Gr.-im- XH; in

i Gkuiit

XJI 3 in

loo 5

1 lit:o

l.V '

‘ KlO

j 1 litie

15'^

1 ofiolulion.

0-99o

1 -]

0-935

17-1

IGO

0-990

2-3

0-930

18-0

173

0-98,")

!}*.“)

0-925

20-2

; 187

0-9S0

4-8

0-920

21-7

t 200

0-97r,

0-0

0-915

n o . o

^ < i »>

' 214

0-970

7-3

0-910

25-0

■ 227

0-9G5

S-G

0-905

2G-G

! 241

0-9C0

9-9

0-900 '

28-3

1 255

0-955

11-3

108

0-895

30-0

2C9

0-950

12-7

^ 121

0-S90 i

31-7

j 282

0-9-15

14-2

134

0-8S5 i

33-7

; 298

0-9-10

15-G

147

0-880 !

i 1

35-G

' 313

Solid “ ammonia i.s commonly known as ammonium carbon-
ate. It is actually a mixture of ammonium hydrogen carbonate
NH.^.H.CO;, and ammonium carbamate NH.j.ISfHo’COo. It is
prepared by heatmg calcium carbonate with a salt of ammonia.

4-1

FERFUMEE T

Commercial samples on titration should contain from 30 to
32 per cent, of NH3.

AMMONIAGUh!. — ^Ammoniacum' is a gum-resin obtained
from the flowering stem of Dorema ammoniacum, a plant found in
Persia and southern Siberia. The stem is pierced by beetles and
the exudation induced of the milivy substance contained in the
ducts in the cortex. The gum-resin contains from 18 to 28 per
cent, of gum, 50 to 75 per cent, of resin, and 0-5 to 2 per cent, of
essential oil.

It is used to a small extent in perfumery together noth
opoponax. The only adulterant usuall}'- found present is the
so-called African ammoniacum, the product of Ferula tingitana,
which maj'- be detected as follows : —

If about 60 grains are powdered and boiled for fifteen minutes
with I oz. of hydrochloric acid, and the liquid cooled and filtered
and then rendered allcaline •udth solution of ammonia, pure
ammoniacum will not show any fluorescence ; whilst if the
African gum-resin be present, the liquid ndll have a blue fluores-
cence. Pure ammoniacum has a specific gravity 1-19 to 1-21, and
the extracted resin has an acid number 69 to 80, and ester number
19 to 38.

The essential oil of ammoniacum has a specific gravity 0-885
to 0-895 ; optical rotation, -j- 1° to 4° ; refractive index, 1-4720
to 1-4810 ; and ester value about 40. It contains linalyl acetate,
citronellyl acetate, a dihydro-sesquiterpene termed ferulene, and
a ketone termed doremone.

AMOMIS JAMAICENSIS. — This plant is the wild pepper
of Jamaica. It jdelds an essential oil consisting largely of linalol.
Its specific gravity is about 0-890. Attempts are being made to
develop the cultivation of the plant. According to the Bulletin
of the Imperial Institute, 1919, 3, 301, the foUovdng are the
characteristics of the oil : —

Specific gravity at 16° .

. 0-8895

Optical rotation at 22°

. —6° 0'

Acid value ....

2-4

Saponification value ' .

4-2

)j ,, after acetylation

. 129-4

Percentage of esters . . ,

1-5 per cent.

„ total alcohols CjoHjgO

. 39-4 „

It is soluble at 15° in 2-5 volumes of 70

per cent, alcohol : the

solution becomes cloudy on the addition of 6 volumes of the same
alcohol.

P El^F V ilf E BY

AMYL ACETATE.— This ester, CH;,.C 00 .G 5 Hjj, is used
more as a flavour tlian a perfuiuc, althougli, judiciously used, it
is very useful in the blending of fruity odours. It is the basis of
artificial oil of jiear, and is j)reparcd by the esterification of amyl
alcohol by acetic acid. Although usually' Icnovn as amyl acetate,
it is actually mainly composed of i'-o-amyl acetate. It has a
specific gravity 0-87G and boils at 138° to M0°.

Ah'IYL ALCOHOL. — The amyl alcohol found naturally in
Bourbon geranium and in certain euc.dyptus oils is iso-amyl
alcohol, or isobutyl-carbinol (Cir^)XTI(Crro).(CTL,OH). It is a
liquid, boiling at 131°, of specific gravity "o-Sl 35, and forms a
phcnyl-urd.lianc melting at 52° to 53°.‘ This alcohol is the
principal ingredient of the amyl alcohol produced by fermenta-
tion, but this is usually a mixture with its isomers, so that the
commercial esters are rarely absolutely pure chemical individu.als,
as they are manufactured from the fermentation pj-oduct. ii'or
the characters of the esters of pure tertiary amyl alcohol (CPbjja.C.
CILOH, see KondakofT {.Jovr. Prahi. Chau.,' 2, 48, 4G7.) The
commercial alcohol has a specific gravity about 0-815 ; refractive
index, 1-4090 ; and boiling point, 130°.'^

AMYL BENZOATE.— This ester, CJ-r..COO.C.njp is pre-
pared by condensing amyl alcohol and benzoic acid by means of
liydrochloric acid gas. It is n poverful fixative, and has a slight
“ amber ” odour. It has a specific gravity 0-094 to 1-003 ; boiling
point, 201° ; and refractive index, 1-4045.

AMYL BUTYRATE, Csirii.OOC.CCILJyCILj. is an ester of
very fruity odour, used in the manufacture of fruit essences, and
to a certain extent in the compounding of floral essences. The
commercial article is a mixture of several isomers, of which the
principal is iso-amyl butyrate. Its specific gravity is 0-8GG ;
boiling point, from 109° to 180° ; and refractive index, -1-4100.

AMYL CAPROATE. — ^This ester, also known as amyl
hexoate, is occasionally used on account of its fruity odour. It
is a mixture of isomers in which iso-amyl capi-onte predominates.
It is a liquid of specific gravity 0-SG4 to 0-867, and refractive
index 1-4210.

AMYL CAPYLATE. — This ester (ani}”! octoatc) is very
similar in character to amjd caproate. It is a liquid of specific
gravity 0-8G3, and refractive index 1-4265. It consists mainly of
the iso-anyyl ester.

PERFU MERY

AMYL FORMATE. — ^TMs ester has a sharp fruity odour.
It consists mainly of the iso-amyl ester, and has a specific gravity
about Q-S80 and boils at' 120° to 125°.

AMYL-HEPTINE-CARBONATE.— This body is one of a
series of esters 'which have a pecuhar, fragrant odour, and which
form the basic material in the perfumes known commercially as
“ vert de violetle.” Theh’ preparation is due to Moureu (French
patent 306619 of 1900, American patents 749800 and 750213).

Heptine is an acetylenic hydrocarbon of the formula CH 3 .CH 2 .
CH 2 .CH 2 .CH 2 .C • CH, It is prepared by various methods, such as
from oenanthol (heptanal), a product of the diy distillation of
castor oil. This is converted into a dichloro derivative by PCls ;
2 molecules of HCl are 'withdrawn successively by aqueous
and by dry caustic soda, leaving heptine. [Vide “ Heptine
Carbonate.”)

Heptine is transformed into heptin-earbonic acid by treatment
with magnesium ethyl bromide and passing a current of carbonic
acid gas tlirough the mixture. The heptine-carbomc acid is
hberated from the magnesium salt thus formed by dilute sulphuric
acid. It has the formula CH 3 .CH 2 .CH 2 .CH 2 .CH 2 .C ;• C.COOH.
It is a hqidd of specific gra'vity 0-969. It is converted into its
esters by warming 'ndth the corresponding alcohol and a small
quantity of strong sulphmic acid. Amyl-heptine-carbonate boils
at 147° to 150° at 20 mm. pressure. The methyl ether boils at
105° to 109° at 20 mm., the ethyl ether at 114° to 117° at 18 mm.,
and the benzyl ether at 184° to 190° at 18 mm.

AMYL HEPTYLATE. — ^This is a fairly new and very expen-
sive synthetic perfume. Its formula is CH 3 {CH 2 ) 5 .COOC 5 Hii. It
is an oil 'with a very powerful fruity odom’, and must be used in
very small quantities, as other-wise its odour will spoil the prepara-
tion it is intended to improve. Its purity may be controlled by
saponifjdng and examiniug the resulting fatty acid, which should
melt at — 10° and boil at 223°.

AMYL PHENYLAGETATE.— This ester has a sweet floral
and fruity odour. Its speciflc gravity is about 0-980 ; refractive
index, 1-4845 ; and boiling point about 265°. It consists mainly
of the iso-amyl ester. /

AMYL PROPIONATE. — ^This ester resembles the acetate
in general characters. It consists mostly of the iso-amyl ester, and
has a specific gravity 0-873 and boils at 150° to 163°.

47 ^

PE nFU MERY

AMYL SALICYLATE. — This is an exceedingly popular
S3nitlietic perfume. It is used to a considerable extent in the
preparation of perfumes of tlie orchid, clover, and carnation t 5 ''pes.
It is sold under such names as “ artificial orchid,” “orchidee,” or
“ trefie.” The experienced perfumer will prefer to buy a pure
amjd sahcylatc and dilute or blend it to his o-wn taste.

It is prejjared by the esterification of amyl alcohol by salicylic
acid, using sulphuric acid as the condensing reagent. It is a
colourless oil of delightfiil odour, having a specific gravity 1*055 ;
refractive index, 1*5050 ; and boiling pomt, 278°.

AMYL VALERIANATE.— TJiis ester, C^Hg.COO.CsHjj, is
IJreparcd in a similar manner to that used for the other am 5 d
esters. It has a powerful apple odour, and is only used in small
quantity in the preparation of fruity odours. It boils at 188° and
is actualty the iso-valerianate, or consists mainly’ of this variety.
Its specific gravity is about 0-8G4, and refractive index 1*4120.

AMYRIS BALSAMIFERA, OIL OF.— The botanical
origin of the so-called West Indian sandalwood oil was quite
unknown until Holmes, Kirkby, and Petersen {Pharm. Jonr.,
1886, iii., 16, 757, 821, 1065) decided that the plant from which
it was distilled could not be considered as belonging to the natm'al
order Sanialacecc. At the suggestion of E. ]\I. Hohnes, Sclninmel
cfc Co. obtained flowering branches of the tree from Venezuela,
and an examination of these led Holmes to the conclusion that
the plant belonged to the natural order Ruiacece. He assumed
it to be an unknovTi species, and named it ScMmmelia oleifera.
It is now agreed, hoAvever, that it belongs to the species Anujris,
and the tree is now loiown as Amyris halsamifera. The wood of
this tree jdelds from 1*5 to 3*5 of essential oil on distillation. It
is a viscid od of heavy aromatic odoim, resembling to some extent
that of the true sandalwood oil. Its characters are as follows : —

Specific gravity . . . 0*950-0*072

Optical rotation . . . + 19° to -f- 30°

Refractive index . . . 1*5080-1*5145

Acid value .... 1-3

Ester value .... 1-6

Ester value after acetylation . 66-125

The oil contains from 27 to 55 per cent, of a mixtm-e of alcohols
of the formula CjsHooO. This mixture was believed by Von
Soden [Pharm. Zeii., 1900, 45, 229) to be a single compound, and
was by him named amyrol. Von Soden and Rojahn [Pharm.
Zeit., 1900, 45, 878), however, then found that it was a mixture

PEBF TIMER I

from ■which at least two alcohols could be isolated. These were
found to have the follovdng characters : —

Formula . , . O15H20O . . C15H24O

Specific gra-vitj’- . . About 0-9S7 . . —

Optical rotation . ’ . 36° . . 0°

Boiling point . . 299° . . Below 299°

The oil also contains a body of the formula O14H12O3, melting
at 117°, which has been named amyroUn ; (Zca;fro-cadinene, and
j3-caryophyllene.

The oil is used in the cheaper tj'pes of perfumed soap, etc.,
where an odom resembling that of sandalwood oil is desired.

AMYROL. — ^Amyrol is probably not an indi'sddual chemical
compound, but a mixture of alcohols which form the principal
odour bearer of the so-called West Indian sandalwood oil. This
oil is distilled from the wood of Amyris halsamifera {vide “ Sandal-
wood OH.”). The mixtui’e of alcohols has the foUo'wing characters :
specific gravity, 0-980 to 0-982 ; optical rotation, 27° ; and
boiling point, 299° to 301° at 748 mm. Van Sodan and Rojahn
{Pharm. Zeit., 1900, 45, 229) claim to have separated this mixture
into two isomeric alcohols, ha'ping either the formula C15H24O or
^15^200 the follo'unng characters : —

Formula .... CisHagO . . C15H24O

Specific gravity . . . 0-987 ^ . —

Optical rotation . . . 4-36° . . 0°

Boiling point . . . 299° . , Below 299°.

ANDROL. — ^This body is an alcohol, isomeric ■with citroneUol,
found in oil of water fennel.

ANDROPOGON IWARANGUSA. — ^This essential oil has
been investigated by J. L. Simonsen {Jour. CJiem. Soc., 1921,
1644). It is of interest in that it was fo^und to contain about
80 per cent, of piperitone, the ketone discovered by Smith in
certain eucalyptus oils (see “ Piperitone ”). The grass occurs in
the Himalayas and outer hill zone from Kashmir to Assam,
ascending to 8,000 feet and above, and in the plains from north-
west Himalaya to Bombay Presidency. The piperitone present
is dextrorotatory.

ANDROPOGON OILS. — ^The principal oils distilled from
plants of the natural order Grwniineoe belong to the family formerly
kno^wn as Andropogon. Much confusion had crept into the nomen-
clature of these plants, but it has been dissipated by Dr. Otto
r. 40

PERFUMERY

Stapf {Kew Bulletin, 1908, 8, 297), who has rearranged the
classification, with general approval and acceptance. (See under
“ Grass Oils (Perfumed) of India and Cejdon,” “ Cymbogon,”
“ Lemongrass,” “ Citronella,” “ Vetivert,” “ Palmarosa,” etc.)

ANETHOL. — ^Anethol CjQHjgO (iso-estragol, Methyl-pam-
oxypropenyl-benzene) is the principal constituent of aniseed and
star aniseed oil, and is also present to a large extent in oil of
fennel. It is a crystalhne body, melting,at 22° to 23°, of specific
gravity 0-985 at 25° ; refractive index, 1-5600 at 25° ; and boiling
point, 234°. It is used to a hmited extent in perfumery, but is
of most importance in the' preparation of anisic aldehyde, a body
generally known as aubepine {g.v.), the basic material for the
preparation of the hawthorn type of perfume.

ANGELICA OIL. — ^AU parts of the Umbelliferous plant
Angelica officinalis {Angelica Arcliangelica) yield essential oils.
The principal of these is that obtained from the fresh root. The
plant is found in Lapland, Sweden, Norway, Germany, etc., and
is cultivated to a considerable extent in Saxony. The oil is used
in the flavouring of hqueurs, etc., and to a small extent in per-
fumery. It usually has a specific gravity 0-855 to 0-920 ; optical
rotation, -f- 16° to + 40° ; refractive index, 1-4770 to 1-4880 ;
and ester value, 12 to 40. Roure-Berlrand Fils {Bulletin, October,
1921, 34) have distilled an oil from the fresh roots which had a
specific gravity 0-8907 ; optical rotation -t- 6° 42' ; and ester
number, 45. The flavouring constituents are not well understood.
Japanese angelica oil is obtained from Angelica anomala, and has
a shght odour of musk.

ANISEED. — Two entirely different plants, belonging to dif-
ferent natural orders, yield aniseed oils which are practically
identical. The true aniseed ofl. is obtained from the fruits of
Pimpinella Anisum (N.O. Umhelliferce). The so-called star
aniseed oil, which forms the bullc of the world’s supply, is the
product of the fruit of Illicium verum (N.O. Magnoliacece). Except
for the fact that the oil from the true aniseed is rather more dehcate
in odour, the two oils may be regarded as identical. They are used
for flavouring to a considerable extent, and to a small extent in
perfumery. The chief value, however, of aniseed oil to the
perfumery industry lies in the fact that it provides the raw material
for the manufacture of aubepine.

The star anise {Badiane) is chiefly found in southern China and
Tonkin. The oil is distilled, principally by natives, and sold to

PERFU MEB Y

mercliants, wlio transfer it to Hong Kong, where it is bought bj’’
exporters and sent thence to Europe and America. Adulteration
Avas at one time very extensive^ practised, chiefly by a group of
Chinese merchants who were known as the Bande Noir, but
to-dav the oil reaches Europe in a state of purity, and is seldom
ji(Jutterated. The process of distillation is as follows. About
20 lb. of the fruit are placed in an iron pan and covered with
water. A second iron pan is placed upon tliis, upside down, so as
to form a cover. The latter vessel is pierced with a circular
opening, over wliich is placed an earthen vessel with three small
orifices in the lower part, which allow the access of vapour. These
orifices are- covered on the inside by small ear-shaped hoods,
which cause the vapour to be spread over the sides of the vessel.
This earthen vessel is covered with an iron pan, which acts as a
refrigerator and into which a continuous current of cold water is
admitted. The joints of the first two iron pans are luted, and the
earthen vessel and refrigerator are jointed -uith cloth bandages.
The vapour reaches the earthen vessel and is condensed when it
impinges against the refrigerator, and falls into a circular trough
at the bottom of the vessel, whence it escapes through a small
pipe. The annual exportation of star aniseed oil varies from
60,000 to 200,000 kg. per annum.

Illickm verum is a small tree, growing to the height of from
8 to 15 metres. The trunk, which is frequently bifurcated at the
base, is from 25 to 30 cm, thick, and rises to a height of 1-5 to
2 metres -without brandling. The leaves are evergreen, the flowers
appear twice a j’ear, and the young fruits are star shaped, w’^hich
gives the name to the tree. The yield of oil varies from 2-5 -fco

5 per cent. The essential oil is, at ordinary temperatures, a solid
crystalline mass having the foUowing characters : specific gravity
at 20°, 0-980 to 0-990 ; optical rotation, + 1° to — 2° ; refractive
index, 1-5530 to 1-5565; melting point, 16° to 19° ; congealing
point, 15° to 17-5°.

The true aniseed, Piinpinella Anisnm, is found in many parts of
Europe, principally, however, in Russia. According to ScJdmmel

6 Co., the following yields are obtained from the fruit as gro-wui in

various countries : —

Chili

1-9 to 2-6

Italy

Per cent.

2-7 to 3-5

Macedonia

2-2

Moravia

2-4 to 3-2

Mexico .

1-9 to 2-1

East Prussia .

2-4

Russia .

2-4 to 3-2

Spain .

3-0

Syria

1-5 to 6-0

Thuringia

2-4

61 1-2

PERFUMERY

In Russia anise is grown in the county of Voronetz in the
districts of Biriutch, Ostrogojsk, and Valuild, and the oil is, as
mentioned above, practically identical with star anise oil.

The following bodies have been identified in star aniseed oil :
f?e.rfo'o-pinene, phellandrene, cymene, cineol, dipentene, limonene,
terpineol, methjd-chavicol, liydrokmone-ethyl-ether, safrol, a
sesquiterpene, anise ketone, and anethol. True aniseed oil has
not been so exhaustively investigated, and the only bodies so far
detected are anethol, methyl-chavicol, anise-ketone, and aldehyde.

The fruit of a plant Seseli HaTveyanum, known in Victoria
(Australia) as aniseed (but which more closely resembles fennel),
has been examined by XJmney and found to contain anethol, but
in considerably less quantity than ordinary aniseed oil. There is
also a false aniseed, IlUcium religiosum, known in Japan as
SMlcimi-no-M. It contains eugenol, cineol, safrol, and a mixture
of terpenes. The principal adulterant of aniseed oil is petroleum
oil. The pm’e oil is soluble in 3 volumes of 90 per cent, alcohol, a
feature which is interfered vdth by the presence of petroleum. So
long as the congealing and melting points of the oil fall within the
limits given above, it is most unlilccly that the oil is adulterated.
It must be remembered, however, that aniseed ofi. is one of those
oils with a considerable tendency to remain in a state of super-
fusion, so that it may be cooled dovm to well below its congealing
pouit vnthout becoming sohd. To determine these temperatines,
a small quantity of the oil should be placed in a narrow test-tube
and cooled down to about 10°. If it does not congeal on stirring
with a small-bulbed thermometer, a crystal of anethol should be
added, when the mass will rapidly crystallise. It should be gentty
stirred, and the temperature rises as crystallisation takes place.
The maximum temperatme is noted, and is taken as the con-
gealing point. The tube is then gently warmed by holding in the
hand, and the contents kept stirred all the white by the ther-
mometer. The temperatm’e at which the crj^stals completely
disappear is taken as the melting point. Oils with congealing
points of 12° to 13°, but which are soluble in 90 per cent, alcohol,
are not lilcely to be adulterated with petroleum, but may be
adulterated with a fraction of camphor oil, or by tlie abstraction
of anethol. An oil adulterated in this manner has been examined
by E. J. Parry {Chemist and Druggist^ 1910, 687). Its characters,
compared mth those of a pure oil, were as follows : —

Adulterated. Pure.

Specific gra\fity at 20° . 0-972 . . 0-982

Optical rotation . . 0° .. — 1° 10'

62 ■ .

PERFUMER Y

Refractive index at 20°

Adulterated.

1-5469

Pure. -

1-5547

Melting point . * .

13°

18°

Congeahng point

11°

15°

Refractive index of first 10 per
cent, distilled

1-516

1-5346

Refractive index of last 20
per cent.

1-540 ‘

1-556

ANISIC ALCOHOL.— This alcohol CRH^CCHaOH) (OCH3)
has been found as a constituent of Tahiti vanilla beans. It is
produced artificially b}'^ the action of caustic potash on anisic
aldehyde. It forms colourless crystals melting at 45°, and boiling
at 259°. It forms a phenjd-urethane melting at 93°.

ANISIC ALDEHYDE. — ^This ai'tificial jrerfume is laio\m
commercially as aubepiiie, or artificial hawthorn. It is a methyl
ether of para-ox 3 '--benzaldehyde, of the formula CgHgOo. It is an
oil having the following characters: specific gravity, 1-1275;
optical rotation, 0° ; refractive index, 1-5730 ; and bo ilin g
point 246°.

Anisic aldehyde is the basic material for all perfumes of the
“ may blossom ” type.

A small amount is obtained as a by-product in the manufacture
of coumarin, but it is usually manufactured on a commercial scale
by the following process. Star aniseed oil is warmed for an hour
or two with three times its volume of nitric acid (specific
gravity, 1-1), and the heavy oil separating is washed vdth potash
solution. This oil is crude anisic aldehyde. It is combined with
sodium bisulphite' by shaking it with a hot solution of that salt,
and the resulting crystals are washed with alcohol, dried on porous
paper, and dissolved in water. It is then warmed with solution
of sodium carbonate, and the resulting anisic aldehyde is separated
and rectified.

Aubepine is also manufactured commercially by treating toluene
sulphonic chloride, a by-product in saccharine manufacture, with
a solution of soda ash at 100°. The p-toluene sidphonate of
sodium resulting is melted with caustic potash, and the resulting
para-cresol hberated by hydrochlorie acid ; this is then esterified
with dimethyl sulphate, and the resulting para-cresol methjd ether
is dhectly oxidised to anisic aldehyde.

The solid aubepine of commerce is the combination of the
aldehyde with sodium bisulphite, but is now seldom employed.

ANISYL METHYL KETONE. — See “ Methoxy-aceto-

lihenone.”

PERFUMERY

ANTHRANILIG ACID ESTERS.— AiitliraiiUic acid, or
ortho-amido-benzoic acid C^H^’NHo'COOH is one "which forms
several higlily odorous esters, of which the most important
naturally occurring compound is methyl anthranilate CfjH.j.NHo
COOCH3. The only other ester of an}’" particular importance is
ethyl anthranilate. Meth 5 d-anthranilic acid also yields similar
esters, of which the methyl ester occurs naturally.

Methjd antliranilate is found m the essential oils of neroli
petitgrain, jasmin, gardenia, and tuberose, frecpiently associated
vith methyl methyl-anthranilatc.

Anthranilic acid is manufactured on a commercial scale by
first oxidising naphthalene by means of fuming sulphuric acid in
the presence of salts of mercury. Forty grams of mercury are
dissolved in 1 kg. of sulphuric acid, and the mixture is heated until
the sulphuric acid distils. To this is gradually added a mixtmre,
prepared three hom's previously, of naphthalene 3-5 kg., suljphuric
acid (66°. B.) 37 kg., and fuming sulphuric acid 10-5 kg. The
phthahe anliydride formed distils over with some sulphuric acid,
from which it is freed by washing. It is finally subhmed, when
it should melt at 128°.

Phthahe acid is melted and brought to a temperature of 140°.
A current of dry ammonia gas is then passed through it, the
reaction temperature being gradually increased to 240°. This
results in the formation of phthahmide CgH.i(CO) 2 NIi. Phthali-
mide is treated "with potassium h 5 'pobromite or hypochlorite in
the presence of excess of aUvah, and anthranihe acid results. On
recrystalhsation the pure acid melts at 144° to 14-5°. There are
several other methods by which this acid can be obtained, but the
above is the most practical. The acid is esterified with methyl
or ethyl alcohol, as the case may be, using hydrochloric acid as the
condensing agent.

Methyl anthranilate CgH^lNHalCOO.CHg is a crj^stalline body
melting at 24°, and boiling at 135° at 15 mm. Its specific gravity
is 1T68. Eth}^ anthranilate is a hquid boiling at 145° at 20 mm.
Both esters have a characteristic neroli odour, that of the ethyl
ester being sweeter and softer.

If methyl antliranilate be heated with methyl iodide and water
for several hours under a reflux condenser, methyl methyl-
antliranilate, melting at 18°, results.

F. B. Power {Jour. Amer. Ghcm. Soc., 1921, 43, 377) has
published a method for the detection of methyl anthranilate in
fruit juice, in which 500 c.c. of the juice are steam distilled

PERF UMER 7

tmtil 200 c.c. have come over, when, if appreciable quantities of
methj^l anthranilate are present, the solution -will show a bluish
fluorescence. At this stage the ester is extracted from the distillate
by three successive quantities of clfloroform of 10 c.c. each. The
chloroform extracts are filtered, and the solutions evaporated on
the water hath. Two cubic centimetres of 10 per cent, sulphuric
acid solution are added to the residue, and the mixture is trans-
fen-ed to a test-tube. During the evaporation of the chloroform
extracts, etc., there is prepared a mixture of 1 c.c. of 0-5 per cent,
pm-e beta-naphthol solution, 1 c.c. of 10 per cent, solution of
sodium carbonate monohydrate NaoCOg-HoO, and 1 c.c. of a
10 per cent, solution of caustic soda. On adding the ester solution
in the test-tube to this mixture, the presence of OT mg. or more
of the methyl anthranilato will be shown by the formation of
yeUowish-red coloration.

Another method is to add a drop of dimethylanihne to the ester
solution, and, when solution results, the addition of a slight excess
of caustic soda will give a yellow coloration, which is changed to
red by the addition of a little dilute acid.

The quantitative determination of methyl anthranilate is best
carried out by the method suggested by Hesse and Zeitschel.
Trom 25 to 30 grams of the sample are dissolved in two to three
times its volume of- perfectly dry ether. The mixtime is then
cooled in a freezing mixture, and then a mixtiue of 1 volume of
sulphuric acid and 5 volumes of ether is added slowly until no
further precipitation takes place. The whole of the methyl
anthranilate is thus precipitated as sulphate. The precipitate is
collected, washed vuth ether and weighed. This gives the
approximate amount of' the ester present. For a more exact
result, the precipitate may be titrated vdth semi-normal potash
solution. If P be the weight of oil employed and N be the number
of cubic centimetres of semi-normal allrali used, then the
percentage of methyl anthranilate is given by the formula

r 3-775 X k

P A. G.

AQUILARIA GRAS SNA. — ^This plant, growing principally
in Cambodia, is liable to be infected with a disease, the nature of
which is not yet understood, which, causes the wood to become
resmous and highly odorous, especially when burned. The wood
is used in the preparation of Chinese joss sticks, and for incense
purposes generally. (Vide La Parfumei'ie Moierm, 1923, 124.)

PERFU MERY

ARMENIAN PAPER. — ^The so-called Armenian paper is an
absorbent paper saturated with an aromatic solution and dried
so that, when burned, it evolves an odour of the type of incense.
The paper is made by making an, alcohohc solution of the following
type

Frankincense- . . . .2 parts.

Storax ...... 2 ,,

Gum benzoin . . . . 2 ,,

Balsam of Peru .... 0-5 part.

Balsam of tolu .... 0-5 ,,

90 per cent, alcohol . . .5 parts.

To this is added sufficient of a saturated solution of potassium
nitrate in water to enable the paper to burn freely, and the
absorbent paper is then soaked in the mixtrue, drained, allowed
to dry in the air, and cut into convenient stri^DS.

AROMADENDRAL. — ^This body is an aldehyde of the
formula CgHigO, isolated by Baker and Smith from various oils
of euealyptus. It has a pleasant odour, resembling that of
cumie aldeh3ffie, with -which Schimmel & Co. consider it to be
identical. It has a specific gravity about 0-950 and boils at about
218°.

ARTEMISIA OILS. — Certain of the oils distilled from
species of Artemisia (N.O. Compositoe) are used to a considerable
extent in flavouring, and to a small extent in perfumery. The
principal of these is the oil of Artemisia Absinthium, oil of worm-
wood or oil of absinthe. The plant is indigenous in the Old World
as far north as Scandmavia, Finland, and Siberia, and appears
to have migrated to North America, It is found wild in some
parts of Great Britain, and is eultivated in the United States,
Russia, Algeria, Corsica, Spain, and Italy. The principal areas
under eultivation in the United States are situated in Wayne
County and in Sauk Count}^.

The eharaeters of the oil vary considerably, according to
vffiether the herb is fresh or dry or in an intermediate condi-
tion.

It is a somewhat viscid liquid, usually of a dark green or blue
colour, but sometimes dark brown. The colour appears to be
dependent on the length of time taken by the distillation.

Gildemeister and Hoffmann (2nd Enghsh ed,, vol, 3, p. 640)
give the follovdng figures for genuine samples of the oil as found
in commerce : —

PERFU 31 EEY

French.

Algerian.

Italian.

American.

Spe ific^praYity,

0-901— 0-954

0-905—0-939

0-918—0-943

0-916—0-938

Eefractive index

1-46684

—

Acid value

Up to 6-7

Up to 6-1

Up to 5-6

Up to 2-2

Ester value

Ester value after

11 to 108

14 to 93

15 to 37

46 to 89

acetylation ,

—

123-2

113-9

Schimmel & Co. distilled a number of specimens of the herb
grown at IMUtitz and at Barreme, and give the following results
for the oOs obtained ; —

Miltitz

Yariety of Herb,

Hungarian.

Miltitz.

French grown in
Miltitz.

Specific gra-vity

Acid value

Ester value .

Ester value after
acetylation

0-8845-0-9125

16-8

35-75-4

0-932-0-954

0 - 2 - 8-6

7-6-85

153-222

0-927-0-933
Up to 1-5
38-8-65-3

93-3-170-3

Barreme

Variety of Herb,

Wild.

Cultivated.

Specific gravity

Acid value ....

Ester value ....

Ester value after acetylation

0-901-0-908
Up to 3-2
34-3-57-4

0 - 936 - 0-939
Up to 2-8
96 - 4 r -114
164-5

An oil distilled from wild Dalmatian herb had a specific gravity
0’9188.; acid value, 1*3 ; and ester value, 64-6 [Schimmel t& Co.,
Report, October, 1911, 101).

E. R. Miller [Bulletin Univ. Wisconsin, 693) has examined six
samples of Wisconsin oils, and found them to contain from 25-8
to 35' 1 per cent, of esters calculated as thujyl acetate, and from
8-9 to 21*6 per cent, of free alcohols as thujyl alcohol.

Charabot [Comptes Renclus, 1900; 130, 923) has shown that
the proportion of thujone to thujyl alcohol in the oil changes as
the plant develops, the thujone being graduallj'^ converted into
thujyl alcohol.

PERFUMEBI

Boure-Berirand Fils {Bulletin, April, 1906, 36) give' the follow-
ing results from two oils distilled from wild plants grown in the
hills round about Caussols (Alpes Maritimes) : —

Esters .

Per cent.

9-0

5-5

Combined alcohols .

. 7-0

4-3

Free alcohols .

. 71-9

76-3

Thujone

8-4

3-0

The oil contains, in addition to thujyl alcohol and its esters,
thujone, phellandrene, cadinene, traces of pinene, and a blue
compound known as azulene. The thujone present exists in two
isomeric modifications.

Artemisia arborescens is a shrub-like plant common to the
Mediterranean countries. Scliimmel & Co. [Report, November,
1908, 136) have examined a sample of the oil which had a deep
blue colour. Its specific gravity was 0-9458 ; acid value, 9-8 ;
and ester value, 19-5. Jona [Ann. Chim. Appdie., 1914, 1, ii., 63)
found 14 per cent, of alcohols present, including thuj3d alcohol
and bonieol, and 13 per cent, of thujone.

Pellim and Morini [Biv. lial, del Essences et del Prof., December,
1923) give the foUovdng characters for this oil : —

■ ■ . _ — - - . . .. 1

Sicilian.

Sardinian.

Calabrian.

Specific gravity

0-9578

0-9458

0-943

Acid number .

9-8

10-5

Ester number .

11-9

19-5

14-33

Ester number after acetylation .

28-6

47-6

Ester per cent.

4-17

6-82

—

Free alcohols per cent.

4-65

8-58

Total alcohols per cent.

7-92

13-94

13-08

Yield per cent.

0-482

0-570

0-200

Artemisia vidgaris is a common weed, which grows along
hedges and road sides, and wliich yields about 0-1 per cent, of
essential oil of specific gravity 0-907. It contains cineoL It
appears, however, that this oU Offers greatly in character, accord-
ing to its place of origin. Two samples, known as yomugi oil
in Japan, which were probably derived from A. vulgaris, were
examined by Scliimmel cb Go. [Report, October, 1903, 78 ; April,
1904, 78), and found to have the following characters : —

Specific gravity . 0-910 . . 0-9126

Optical rotation . —13° 16'" .. — 18° 50'

68 "

perfumery

: ttr j-f®’

Ester value . . 29-8

examined at the Imperial Institute under the name

tion value 108-q- -a 0-939 ; sapomfica-

2 .

- - 0-949 (at 20°)

Specific gravity
Optical rotation
Eefractive index
Acid value . .

Ester value
Ester value after
acetylation

— 8° 52'
1-4620
1-2
22-1

+ 57° 2'

- ' ' 55-5 ^ ^ 228

(See also ScUmmeVs Report, Koyembor, 190S, 140.)

0.9.ra:,“

Artemisia (?fefe‘?i05a.— Bennett (P. & E O T{ loon - oo,.^
lias examined the essential oil dist lied from SSs 2/"’ i

Specific gravity
Optical rotation
Refractive index
Total alcohols as borneol
Esters as bornyl acetate
Phenols . . , ' '

. Aldehydes and ketones , jg

- Eor other artemisia oils, see E J Parrv " Ti <a r<u ” • jl
Essential Oils, etc.” (4th ed., vol 2 p 29^’ 7 Chemistry of

Oil/’ » Gougt, Oil of,” and » Scinch, Oil of!”

artificial esters in ESSPKrTTAT r^rr ^

artificially prepared and are '5’'’°'* *° ““

to raiee esr/aCofX ofl ” “ -^er

0- 937
+ 24°

1- 4780

17-5 percent,
6-3 „

PERFUMER Y

As it has become the custom to value certain essential oils,
such as lavender, bergamot, etc., b}^ their ester content, the
detection of the addition of these artificial esters is of importance.

The prmcipal esters used for this piu’pose are terpinyl acetate,
gtyceryl acetate, ethyl citrate, ethyl succinate, ethyl tartrate,
ethyl phthalate and ethyl laurinate.

Them boiling jDoints and sjDecilic gravity are as follows : —

Acetine .
Monacetine
Diacetine
Triacetine
Ethyl citrate
Ethjd succinate
Ethyl tartrate .
Eth 3 d phthalate
Eth 3 d laurinate.

Boiling point.

261°-264° C.
Decomposed
2G0°-265° C.
258°-260° C.
28G°-289° C.
212°-218° C.
278°-282° C.
290°-293° C.
270°-310° C.

bpeciuc gravity
at 15 -5° C;
M9
1-21
1-184
1-1G5
1-140
1-044

1-124
0-8GG

the detection

It is impossible to outlme a general method for
of artificial esters, but, as a rule, tlie 3 ’' can be partially separated
by fractional distillation, and then b37' comparmg the ph 3 '-sical
characters of the last fractions with those obtained from oils of
knovui purit 3 '’, indication of the presence of abnormal con-
stituents may usually be obtained.

B 3 '’ saponifying the high-boiling ester-containing portion with
alcoliolic potash, neutralising vdth acetic acid, evaporating the
alcohol, and extracting the oily matter by shaking with ether,
abnormal potassium salts may be detected in the aqueous portion
by evaporating to di’3mess, dissolving in water, and applying the
usual chemical reagents, such as barium chloride, calcium chloride,
ferric chloride, etc.

As a test for the presence of esters of non-volatile acids, such
as citric, tartaric, succinic, and particularly plithalic acid, the
test devised by Bennett (P. cb E. 0. R., 1923, p. 359) is extremely
useful. Tills test is carried out as foUows : —

One cubic centimetre of the oil for examination is placed with
3 c.c. of an approximately 10 per cent, solution of caustic potash
in dbsohite alcohol in a test tube, the whole immersed in a water
bath for a few minutes, and then allowed to cool. If no precipitate
forms ivithin one hour at the most, the oil may be considered
unadulterated with these esters.

Another method by which the presence of non-volatile acids
can be detected has been devised by Messrs. Schimmel {ScliininieV s
Bericht, October, 1910, p. 43 ; April, 1911, p. 151).

PEBFU MERY

This test depends on tlie fact that the esters natural present
in essential oils are esters of volatile acids ; if the ester number
of the oil be determined in the ordinary way, and the mixture
then made acid and steam distilled, the distillate should require
almost the same amount of standard allmli for neutralisation
as was absorbed in determining the direct ester value ; a difference
of more than 10 in ester number between the two titrations
indicates the presence of esters of fixed acids.

This method has been the subject of various criticisms (P. cC*
E.O.R., 1914, p. IIG; 1923, p. 293; iSchimmcl's BerkJif, 1924,
p. 123) and modifications, but it is nevertheless an extremely
useful one. It is, however, likely to give inconclusive results
uhen lauric esters are present, as these are somewhat volatile in
steamJP. * E. 0. R., 1919, p. 17e ; Schimmers BericJil, 1924,
p. 125), and thej’ are best detected bj"" a special method, which
will be described later.

Ghjccnjl Acclate. — ^This adulterant is usually a mixture of
glycciyl acetate in which triacctine predominates.

Its detection is comparatively’- easy, as it is soluble in warm
water, and also in 5 per cent, alcohol solutions.

Messrs. Scliimmcl {SchimmeVs Report, October, 1910, p. 61 ;
April, 1911, p. 150) have iH’oposcd the folloufing method for its
detection : —

Ten cubic centimetres of oil and 20 c.c. of 5 per cent, alcohol
are well shaken in a separating funnel, and after the solutions
have separated and become clear, the watery solution is run off
and filtered. Ten cubic centimetres of the filtrate are exactly
neutialised -uith decinormal allcali, and 5 c.c. of semi-normal
allcali run in, and the whole saponified undei* a reflux condenser
for one houi’. In the case of a pure oil, O-l or, at most, 0-2 c.c.
of semi-normal alkali will have been used up by the saponification,
w'hilst each 1 per cent, of glyceryl triacetate jwesent in the oil
will be represented by practically 0'5 c.c. of semi-normal alliali.

glyceryl acetate is so easily’- washed out with hot water, a
simple method {P. di E. 0, R., 1912, p. 275) is to wash the oil
several times until hot water. When the oil is adulterated, the
washed oil unll show a distinctly lower ester value than the
original unwashed oil, while in the case of a pure oil the ester
value of the washed oil is practically the same as that of the
"unwashed oil. A difference in the refractive indices of the washed
and original oils will also be found when this adulterant is present.

Hall and Harvey (P , tfc E, 0. R,, 1913, p. 6) determine glyceryl

PERFUMERY

acetate in essential oils by a method in wliich the glycerol is
separated and weighed.

T-erpinyl A cetaie. — ^This ester is hydrolysed with . greater
difficulty than the usual natural esters present in essential oils,
and Messrs. Scliimmcl {ScIiimmeVs Report, October, 1910, p. 60)
have devised a method for its detection, based on this fact.

This method is to saponify for one hour and two hours, using
only half the amount of semi-normal allcali for the one-hour
saponification that is used for the two hours’ saponification. In
the case of pure oils, the difference between one hour and the
two hom’s’ saponification values should not amount to more
than 3 ; if 6 per cent, of terpinyl acetate is present, a difference
of as mirch as 14 is sometimes found.

Laurie and oilier Fatty Esters. — ^These esters give no precipitate in -
Bennett’s test, and as some of them are somewhat volatile in steam,
they are not easily* detected by ScliinimeVs method for detecting
non-volatile fatty acids {SchimmeVs Bericlit, October, 1910, p. 43;
April, 1911, p. 151, 1914, p. 125 ; P. E. 0. R., 1919, p. 175).

In order to detect these esters, it is best to sejDarate out the
fatty acids, and this is carried out as follows ; —

Ten cubic centimetres of the oil are saponified for one hour
with 20 c.c. of 2/N alcoholic potash. Twenty-five cubic centi-
metres of viator are then added, and the bulk of the alcohol is
evaporated off. The solution is then almost neutralised to
phenolphthalein, and the unsaponified oil removed by shaking
out tlu’ee times with ether.

The aqueous solution is then made acid to methyl orange, and
shaken out with ether.

The ethereal solution wiU now contain acids, such as benzoic,
cinnamic, oleic, phthahe, and lauric, and these vdll be obtained
in a moderatel 3 ’- pure condition by evaporating off the ether.

M. S.

ASAFCETIDA. — ^This substance is a foul-smelling gum-resin
which, ui an extremety diluted condition, is of value both as a
flavour and as a perfume. It is obtamed as an exudation from
the cortex of the stem and root of various species of Ferula,
prmcipally F. fostida, F . scorodosma, and F. narthex. Its popular
name is “ Devil’s dimg.” It is used in the form of a tmeture in
70 per cent, alcohol. Its jDrincipal constituent is the feruhe ester
of asaresinotannol. A good sample should not contain more than
10 per cent, of ash (earthy matter), the best samples contahiing
from 3 to 5 jDer cent. It yields an ’essential oil consisting principaUj’’

PERFU MER Y

of all}-! sulphides, and having a specific gravity 0-915 to 0-993 ;
optical rotation, + 10° to — 36° ; and refractive index:, 1-4940
to 1-52G0. (Refer Unmey and Bunlcer, P. E. 0. R., 1910, 165.)

ASARUM GANADENSE, OIL OF. — ^The rhizomes of the
Canadian snakewood plant {Asarum canadcnse) yield 3 to 5 per
cent, of essential oil having a specific gravity 0-950 to 0-952 ;
optical rotation, — 2° 50' to — 10° 40' ; and refractive index,
1-4850 to 1-4S90. It contains pinene, linalol, borneol, terpineol,
geraniol, methjd-eugenol, fatty acids, and a lactone of unlcnown
constitution. Its odour is pungent and aromatic, recalling
patchouli and ginger. It is used in the United States for giving
a special “ note ” to cau de Cologne.

ATTAR OF ROSE.— See " Rose.”

AURANTIENE. — ^This name is given to the terpenes of
orange oil, produced in the manufactm-e of terpeneless orange oil.
It consists of limonene, principally in the dextrorotatory form.

BACKHOUSIA OILS. — BacJchousia citriodora, a small tree
growing in Queensland, yields about 1 per cent, of an essential
oil of pleasant verbena odour, which is used in perfumer}’’ to some
extent, but which is now onl}’’ produced on a small scale, o^ving
to the fact that lemongrass oU, which it closely resembles, is sold
at a cheaper rate. The oil contains from 90 to 95 per cent, of
citral {vide “ lonone ”). It has a specific graAity 0-895 to 0-900,
refractive index 1-4860 to 1-4889, and is optically inactive.

Bachhoiisia myrtifolia also jields a pleasant-smelling essential
oil, of -wLich the principal constituent is the phenol ether elemicin.
It has a specific gravity 1-026 to 1-057.

BacHiousia angusiifolia jdelds an essential oil of pleasant- odour,
w'hich contains about 60 per cent, of a body w’hich is probabty
a phenol allied to tasmanol and leptospermol. It has been
investigated by A. R. Penfold, of the Technological Museum,
Sydney {Jour. Roy. Soc. N.S.W., 57, 300). A yield of 1-05 per
cent, on the dried leaves and terminal branchlets w’as obtained.
The oil is of particular interest, since it differs materially from
any Baclchousia oil hitherto described, and contains about 75 per
cent, of a hitherto undescribed - bodj’, which appears to be a
phenol. Dextro-a-pinene, ^-pinene, cineol, a-tei’iDineol, sesqui-
terpenes, and a solid body — probably a lactone — melting at 118°
to 119 'W’ere also identified in the oil. The principal constituent
is a somewhat remarkable compoimd, and appears to belong to

PBB F IJ ME B 7

the grouj) of Ijoclies of which tasmanol and leptosperinol are
recognised constituents. Pcnfold classes it tentatively as a
phenol. Pour oils also examined had the following characters : —

Specific gravity

1-0414

1-0272

1-0042

0-9599

Optical rotation

-f 1-55°

0°

— 1-2°

+ 0-6°

Befractive index

1-508G

1-4973

1-4886

1-4790

Acid number .

203

198-3

— -

Ether number .

216-6

207-1

181-1

Ester number after

acetylation .

225-7

257-1

213-1

, ■

Phenols .

75 per

60 per

26 per

cent.

After extracting the phenols with a caustic soda solution, the
non-phenolic residues resembled eucal^yptus oil in odonr, and had
the following characters : specific gravit}^ 0-903 to 0-90S ; optical
rotation, + 6-1° to -|- 8-25° ; refractive index, 1-4655 to 1-46GS ;
cineol, 30 to 50 per cent. This portion of the oil was used for
the determination of the various constituents mentioned above.
The stearoptene was ciystallised from alcohol, and melted at
118° to 119°. The formula appears to be CjgHjnOg, which was
confirmed bj'- crjmscopic determination of the molecular weight.
The phenolic constituent is a viscous liquid, giving a brilliant
orange colour with ferric chloride, and is slightly Icevorotatory.
Its formula is probabty CioHj,j 03 , and its characters are given
in the following table. Pom’ different specimens are included
from different sources, and obviously traces of impurities are
present in some of them, especially No. 1.

Boiling point,

10 mm. .

122°-124°

123°-125°

123°-124°

122°-124°

Specific gravity .

1-1054

1-0900

1-0848

1-0885

Optical rotation .

— 0-55°

-4-65°

— 4-65°

— 4-45°

Befractive index .

1-5288

1-5130

1-5084

1-5113

Backlioiisia sciadophora jnelds an oil of specific gravity about
0-880, and optical rotation -}- 34°. It consists in the main of
pinene (80 -to 85 per cent.), a sesquiterpene, a sesquiterpene
alcohol, a phenol, and caprylic acid in the form of esters.

BALM OF GILEAD. — ^This balsam, also Imown as Mecca
balsam, is the product oi 'Ealsamodendron GUeadensc or B. Op)o-

P E RF U 21 E B Y

baUaym^n, the former plant probably being a variety of the
latter. The tree is found principally in Arabia. An interesting
historical account of it is given by de Sacy C Relation' de
PEgypte/*’ Paris, 1810). It '^as cultivated — and it^ is very
difficult to cultivate — ^in a garden at Matriya, near Cairo, from
the eleventh up to the seventeenth century, where it was so valued
that the garden was completely walled in and was guarded by
janisaries. Abd-ul-Latif {obit 1231) gives an account of the
preparation of the balm. Incisions were made in the bark down
to the wood (apparently to injure the cambium cells and induce
a pathological secretion), and the juice exuding was scraped from
the tree and preserved in bottles, which were buried in the earth
for a time, and afterwards exposed to the sun until the balsam
had separated from the impurities. It was then subjected to some
secret process, and finally stored in the royal treasury. In lo60
only nine or ten trees remained alive in this garden, and no balsam
was yielded by them. The last tree perished in 1615 tlirough an
inundation of the Nile. It now grows in Arabia, in the neighbour-
hoods of Medina and Mecca. About the beginning of April the
trees drop their juice from cuts made in the smaller branches.
An inferior balsam results from boiling the twigs and skimming
off the floating material from the water.

The genuine balsam, which is very rarely found in commerce,
is at first turbid and white, but thickens with age and becomes
of a honey colour. It is adulterated with turpentine, Chian
turpentine, Canada balsam, and common rosin. Having a low
acid value, it does not solidify when triturated with an eighth
part of its weight of magnesia, as do most of the pine resins. A
reasonably fresh, pure Mecca balsam should have an acid number
of about 40, and an ester number about 100. It is used in the
manufacture of some Oriental perfumes.

BALM, OIL OF.— Oil of balm, or melissa oil, is distilled
from the herb Melissa ojjicinalis, a plant belonging to the natural
order Labiates • It is a native of western Asia, and is fairly widely
distributed. The name is derived from the Greek melissa^ a bee,
and is indicative of the attraction the flowers have for bees on
account of the saccharine matter they produce on a considerable
scale, and which suits the bees for the secretion of honey. The
leaves have a pleasant odour recalling lemongrass and citronella.
The essential oil is scarcely a commercial article in the pure
state, as the yield obtained will not allow the oil to be sold
remuneratively. It is a liq^uid of specific gravity about 0*895 to

p 65 , ^

PERFUMERY

0'925, and contains citral, citronellal, geraniol, linalol, and
citronellol. The oil of balm of commerce is either lemon oil
distilled over melissa leaves, vitli a little citronella oil added, or
the melissa leaves are omitted and the oil is entirely factitious.

BALSAMS. — ^The term “balsam” is an inexact and elastic
one, and is incapable of scientific definition. From the point of
view of the perfumer, the aromatic balsams may be taken to be
oleoresinous exudations of plants, sometimes normal, sometimes
pathological, often containing oifiy very little essential oil, but
always containing odoriferous '^constituents, most frequently
benzoic or cinnamic acids or their esters. Commercially the term
is usually restricted to exudations from the plant, but scientifically
there is no reason to distinguish between these exudations and
aromatic oleoresins extracted from the plant by solvents. Such
bodies are benzoin, storax, balsam of Peru, balsam of Tolu,
labdanum, etc., all natural exudations ; and such bodies as oak
moss or orris resin, oleoresins obtained by extraction vdth
solvents. Most of this group of bodies — ^indeed, practically all
of them — are of the greatest value as fixatives, subject to this
qualification. If an oleoresinous material has a strong and
pronounced odour, it can only be used as a fixative where its
odour will blend with the other perfumes used, unless it be so
' powerful a fixative that verj^ small quantities can be employed.
Apart, however, from this characteristic of these substances, most
of them are highly odorous, usually having a heavy odour of the
so-called Oriental type, for which class of perfumes ■ they are
invaluable as actual odour bearers, apart from their fixative
value. (See also “ Fixatives.”)

BALSAMO BLANCO. — ^This substance, Imown also as White
balsam of Peru, is said to be obtained from the fruit pods of
Myroxylon Pereirce. Germann, however, states that this product
differs from the wliite balsam of Peru which he has exa min ed, and
considers it may be identical vdth American storax from Liqui-
damhar styraciflua. It rarely finds its way into commerce to-day.

BALSAM OF PERU. — ^This substance is of the greatest
value in the preparation of heavy odom’s of the Oriental type. It
is also much valued as a fixative. It is an oleoresinous liquid,
of the consistency of a thick syrup, obtained from the trunk of
Myroxylon Pereirce, a leguminous tree growing in the forests of
San Salvador, in South America. The secretion is not a natural
one, but is pathological, being induced by the gentle heating, and

PERFU MEJ^l

then scorching, of the bark. As the liquid exudes it is soaked up
by cloth, -with which the wounded places are covered. The cloths
are pressed and boU’ed with water, and the balsamic liquid is
separated, and is then ready for export.

Balsam of Peru is a dark, reddish-brown liquid of great viscosity '
and of a penetrating and very sweet odour. It contains from
55 to 65 per cent, of a substance known as cinnamein, which,
however, is not a definite chemical individual, but is a mixtm’e of
esters of both cinnamic and benzoic acids. It also contains a
small amount of free aromatic acids and alcohols, and a trace of
va nillin . The alcohols combined vdth the aromatic acids are
principally benzyl alcohol and peruviol.

When pure the balsam has a specific gravity 1'1400 to 1-612,
refractive index 1-5800 to 1-5855, and contains from 50 to 65 per
cent, of cinnamein, which can be estimated in the following
manner. One gram is dissolved in 30 c.c. of ether and extracted
twice with seminormal aUcali, the aUcaline solution being washed
with ether and the ethereal liquids combined. The ethereal
residue is dried and weighed. This residue, cinnamein, should
have a saponification value of 235 or over.

There is on the market a certain amount of artificial balsam of
Peru, which is of far less odom- value than the natural balsam.
It is stated (British Pharmaceutical Codex, 1923, p. 173) that
this can be detected by the following reaction. Two grams of
the sample are shaken with 10 c.c. of petroleum spirit, and the
petroleum solution is evaporated in a porcelain dish. The residue
is dried on a water bath, cooled, and mixed with 2-5 c.c. of nitric
acid of specific gravity 1-38. The pure balsam gives only a golden
yellow colour. Dieterich (“ Analysis of Resins,” Scott, Greenwood
& Co., London) gives the following values for three samples of
' authentic origin : —

/ 1

Acid value .

77-46

76-92

72-34

Ester value .

165-61

137-42

137-67

Saponification value

243-07

214-34

215-01

Cinnamein .

71-4 per cent.

77-6 per cent.

73-6 per cent.

Resin esters

15-7 „

13-2 „

17-3

Insoluble in ether

^•38 „

4-31 „

3-57 „

BALSAM OF TOLU. — ^Balsam, of tolu is an aromatic,
fragrant resinous material obtained . from artificially -made in-

67 ■■ 5-2

PEBFU MERY

cisions in the trunlc of Myroxylon idluifera, a tree indigenous to
New Granada. When in the fresh condition it is a soft, tenacious
mass, which becomes harder on Iceeping, and is in cold weather
quite brittle. A fragment warmed and pressed on to a microscopic
slide by the cover glass exhibits crystals of cinnamic acid under
the microscope.

It contains the benzoic and cinnamic esters of benzyl alcohol,
free cinnamic and benzoic acids, traces of vanillin, and esters of
a complex alcohol which has been named tolm-esinotannol. A
very small amount of an essential oil is also present.

Balsam of tolu is adulterated, either by the addition of other
resinous matter, or by the abstraction of some of its odorous
constituents. A pure balsam should yield not less than 90-
98 per cent, of soluble matter to 90 per cent, alcohol, and under
10 per cent, to jretroleum spirit.

A pure balsam, should jdeld a distinctly crystalline residue to
carbon bisulphide. This residue should Aveigh at least 25 per cent,
of the weight of the sample.

Common rosin may be detected by exhaustmg 5 grams AA'ith
petroleum ether and shaking the filtered solution with an equal
volume of a 0-1 per cent, solution of acetate of copper.’ In the
presence of colophony the petroleum ether Avill be coloiu'ed a
brilliant green, due to the soluble copper salt of abietic acid.

A genuine balsam of tolu should have an acid value from 92
to 135, and an ester value of 59 to 91.

Delphin {Svenslc. Pharm. Tidskr., 1907, 3, 415) recommends
the folloAving method of anatysis. Taa^o grams are dissolved in
25 c.c. of ether, and normal solution of KOH is added. After
shaking, the aqueous liquid is run into a flask, the ether v^ashed
with a httle water, and the Avash Avater added to the original
aqueous liquid. The ethereal solution is OA’^aporated on a water
bath and exposed over sulphuric acid in a desiccator for eighteen
hours, and Aveighed. This gives the cinnamein, Avhich should be
not less than 8 per cent. The aflcahne liquid is treated AAuth sodium
bicarbonate until an abundant precipitate is formed, and a
current of COo is run tlirough the liquid for an hour. The solution
is filtered, and the precipitate Avashed Avith Avarm AA^ater to remove
aUcali. This precipitate is dried to constant Aveight, and gives the
resin esters. The filtrate from the resin esters is treated AAdth
6 to 7 c.c. of hydrochloric acid, and the resin acids collected on a
tared filter, washed with water, dried and weighed. The weight
should not exceed 1 per cent. The filtrate is extracted Avith ether

PERFU M E R Y

and the ctliereal extract titrated with decinormal potash, with

phenoljjhthaleui as indicator. One cubic centimetre of -J q alkali

corresponds •Rith 0-014S gram of cinnamic acid, which should be
present to the extent of 25 per cent, at least.

According to Cocking and Kettle (see P. cfc E. 0. R., 1918, 202),
the method of the British Pharmacopoeia, 1914, for the estima-
tion of the balsamic acids in balsam of tolu is unsatisfactory, as
much of the aromatic acid present is combined with resin alcohols
and is insoluble in, and thus not extracted b}’’, carbon disulphide.

In 1914 the authors described a process for the evaluation of
benzoin by which the balsamic acids could be separated from the
resinous matter, and the free and combined benzoic and ciimamic
acids determined {Year Boole of Pharmacy, 1914, p. 355), and
this process is now modified to meet the case of tolu balsam.
Boiling out of the aromatic acids vTith magnesium oxide and
water, in the presence of a small quantity of xylene to soften the
resmous matter, was found to be the most satisfactory way of
dealing vith the balsam. The magnesium salts of the aromatic
acids are readily soluble in cold water, those of the resin acids
being insoluble. A complete separation is effected, and the
aromatic acids are obtained in a pm’er condition than by aqueous
extraction alone.

The mode of procedure is as follows : —

(1) Free Balsamic Acids. — ^Five grams of the balsam are
dissolved in 25 c.c. of hot alcohol in a 250 c.c. COo flask, 5 grams
of light magnesium oxide and 20 c.c. of xjdene are added, and the
flask shaken round until the contents are well mixed. One
himdred cubic centimetres of water are now added, the flask
connected to a reflux condenser, and boiled for one hour. After
coolmg, the whole is poured on a Buchner Alter, and the aqueous
portion of the filtrate separated from the xylene layer, which is
returned to the flask together with the Alter paper and adhering
magnesia-balsam magma. A second 100 c.c. of water is added
and the flask again boiled for an hour, when the aqueous portion
is separated as before and the extraction carried out a tliird time.
The bulked aqueous liquids are washed once with 20 c.c. of ether,
then rendered acid with hydrochloric acid, and the precipitated
acids extracted by shaking out with ether. The greater part of
the ether is distilled off, and the residual aromatic acids dried in
vacuo over sulphuric acid, and weighed.

(2) Total Balsamic Acids. — 2-5 grams of the balsam are saponi-

PERFU M E R r

fied by boiling with excess of alcoholic potash ; most of the alcohol
is then evaporated off, the residue dissolved in 100 c.c. of hot
water, and sufficient hydrochloric acid added to render the whole
slightly acid. Five grams of light magnesium oxide and 20 c.c.
of xylene are next added, and the whole boiled up under a reflux
condenser for one hour. The aqueous Hquid is separated, the
extraction twice repeated, and the buUced aqueous liquids treated
as in the case of the free balsamic acids.

The proportion of cinnamic acid is determmed by the gain in
weight on bromination, details of which may be found in the
previous note [Year Booh of Pharmacy, 1914, p. 355). ..

The aromatic acids obtained from balsam of tolu are not quite

Ko.

Acid

Vnluc.

Ester

Value.

Saponifl-

cation

Value.

Per cent.
Free Ben-
zoic Acid,

: Per cent.
Free Cin-
namic
Acid.

Per cent.
Combined
Benzoic
Acid.

Per cent.
Combined
Cinnamic
Acid.

Per cent.

Total

Bal-amic

Acids.

111-8

71-2

183

8-55

I 11-99

G-19

5-93

32-66

112-3

191-3

9-12

11-53

7-87

6-56

35-08

98-1

79-1

177-2

8-48 1

> 11-86

8-35

8-68

37-37

72-2

172-8

7-8 ’

' 10-69

7-45

8-92

34-86

118-2

60-8

179

9-1 j

13-7

5-94

8-97

37-71

92-2 !

62-6

154-8

6-63 1

12-4

6-17

8-67

33-87

101-3

65-9

167-2 1

8-29

13-71

5-37

10-13

37-5

59-3

163-8

8-34

13-54

5-22

9-08

36-18

96-6

65-0

161-6

7-86

13-12

6-43

9-95

37-36

132-4

66-2

198-6

7-42

15-9

11-1

5-2

39-86

39-4

179-5

—

24-74

124-3 !

58-3

182-6

—

24-4

117-8

—

47-56

85-3 1

—

45-12

so pure as those from benzoin. The brominated acids from tolu
are slightly brown in colour, and contain a substance which is
extremely pungent and lachrymatory.

Balsam of tolu, as a rule, contains very little that is not soluble
in alcohol, but occasionallj’’ samples are met mth containing
woody matter. Three sucli samples contained l-G, 8-9, and 9 per
cent, of insoluble matter.

Moistm’e, generally present, was estimated by spreading in a
thin laj^er on a sheet of glass and drying in vacuo over sulphuric
acid. Amounts varying from 2 to 8*6 per cent.. were found, and
the dried balsam was usually quite brittle.

The determination of the acid value of the balsam is somewhat

PERFUMERY

difficult, ou’ing to the dai’k colour and to the precipitate wliich is
formed on running in the alcoholic potash. We find it best to
proceed as follows : —

Dissolve 5 grams of the balsam in about 50 c.c. of boiling alcohol,
add a large quantity of phcnolphthalein solution — 3 or 4 c.c. —
titrate the hot solution ■ndth normal alcoholic potash until the
colour becomes dark brown (but not red), then attach to a reflux
condenser, boil uj) for a few minutes in order to break up the
precipitate, and finish the titration.

By this method titrations agree to about 0-2 c.c.

j KOH.

The variations from a large number of samples of balsam
examined during the last few years ai'c shown in the table on
p. 70.

Excluding numbers 11 and 12, which, from their low content of
balsamic acids, are probably sophisticated, the figures indicate a
range of —

92-2 to 132-4 for acid value,

69-3 to 90-9 for ester value,

154-8 to 208-7 for saponification value,
and 32-68 to 47-50 per cent, of total balsamic acids.

The pharmacopoeial limits for acid value are from 107-4 to
147-2, and for saponification value 170 to 202.

Judged by these figures, numbers 3, 4, G, 7, 8, and 9 would be
rejected for low acid values ; also the saponification values of
numbers 6, 7, 8, 9, and 13 lie outside the limits, although the
poorest of these balsams contains 33-87 per cent, of balsamic
acids. On the other hand, numbers 11 and 12, though abnormally
low in balsamic acids, would bo admitted as genuine.

BANDOLINE. — name given by Erench perfumers to sub-
stances used to -keep the hair fixed when it has a tendency to
straggle.” They are usually perfumed mucilages, preferably of
gum tragacanth, but sometunes of gum arable or quince mucilage.
As they are liable to decompose, a little salicylic or boric acid is
usually added to preserve them.

DARIUM-- sulphate. — ^T his substance, Imown as barytes,
and also as blanc fixe,’' is used to a small extent in some

of- the cheaper types of face powders or enamels. It occurs
naturally as a mineral, but as it must be in an exceedingly fine
state of subdivision for use in the perfumery industry, the natural
substance is not so suitable as an artificially precipitated sulphate,

P E P P IJ M E P Y

wliich is obtained as an impalpable powder. One of the most
suitable forms of this article so far as this point is concerned is the
by-product obtained in the manufactm'e of hydrogen peroxide.

BAROSMA VENUSTA, OIL OF.— From the leaves of
Barosma vennsta Goulding and Roberts {Jour. Clicm. Soc., 106,
2613) obtained 2 per cent, of an essential oil having an agreeable
aromatic odom’. It contains m 3 n’cene, estragol, linalol, aldeh 3 '’des,
sesquiterpenes, and a small quantity of esters and phenols. It

has the folloving characters : —

Specific gravity ..... O-SGo
Optical rotation . . . . +0° 47'

Acid value ..... 5-6

SajDonification value . . . 6-2

Saponification value (after acetylation) 55

BASIL, OIL OF, — Sweet basil oil is distilled from the entire
fresh plant Ocimuui hasilicum. It is a plant of the N.O. Lahiaics,
growing in Europe, northern Africa, Reunion, Java, and Algeria,
etc. The oil is of a fragrant odour, and is of use in the preparation
of perfumes of the types of violet, mignonette and jonquil, etc.

There are several varieties of the plant, wliich has been veiy
completely investigated bj’' E. G. and C. Camus {Bour e-Bertrand
Fils, Bulletin, October, 1910, 23). Of these the most suitable for
cultivation is the variety Crispum, The following are representa-
tive characters of the oils from the principal varieties : —

Specific

gravitj*.

Rotation.

Refractive

index.

Thyrsiflorum .

0*916

- 11°

1*488

Crispum

0*912

— 10°

1*484

Album ....

0*898

— 13°

1*479

Purpurascens

0*896

- 14°

1*477

A normal oil distfiled in Europe (French or German) has a
specific gravity 0*900 to 0*930 ; optical rotation, — 6° to — 20° ;
refractive index, 1*4800 to 1*4960 ; and ester value, up to 12.
Basil oil from Mayotte has a specific gravity 0*960 to 0*967, and
optical rotation about -j- 1°. Basil oil from Java has been obtained
by distilling the large-leaved variety, which is known locally as
Selasih melcaJi. It contained about 30 to 40 per cent, of eugenol.
A sample distilled in the Seychelles {Bidl. Imp. Inst., xvi., I., 30),
had a specific gravity 0*962 ; optical rotation, + 0° 50' ; refractive

P B R F U iU E Ji 3’

index. 1-.31-J0 : and ester mimbcr, 2-5. The European distilled oil
contains methj-l-cliavicol (estragol), linalol, cineol, pinene, and
camphor. Besides the above, several other species of basil yield
fragrant essential oils, of which the following are the pimcipal
Ochrtimi caiunii is a native of Madagascar, East Indies, Cliina,
and Brazil. A sample of the oil distilled from material grown at
Dakalba (Ivory Coast) has been examined by Bourc-Bcrlraml
Fils {Bulletin, October, 1913, IS). It is an oil of pleasant odour,
and is somisolid at ordinary temperatures. It has the foUov ing
cliaractcrs : specific gravity at 32°, 1-033 ; optical rotation,
— 2° 30' ; and saponification value, 301. Its cliief constituent is
jnethj'l cinnamate, which causes the crystallisation of the oil.
Ocinnnn gi'atissiviuvi is a native of Bengal, Chittagong, Nepal, and
the Dcccan. It is a plant whose leaves have a remarkably pleasant
-lemon odour. It is found in native gardens and round about the
temples of the natives. It is found also on the Ivorj' Coast, and
a sample distilled at Dakalba, and examined by Boui'e-Bcrlrand
Fils {loc. cit.), was found to have a specific gramty 0-910, and
optical rotation 1°. It contains thymol and carvacrol. A
sample distilled in the Seychelles {Bull. Imp. Inst., xvi., 1, 30)
had a specific gravity 0-995 ; optical rotation, — 14° ; and
refractive index, 1-5200. A sample of the oil from tliis species
has also been reported on by the Imperial Institute {Bulletin,
vol. xxii., 3, 1924), and found to have the following characters :
Sx}ecific gravity .... 0-996

Optical rotation ....

Befractive index .... 1-5320

Phenols 55 per cent.

and, according to Roberts {Jour. Soc. Cliein. Inch, 1921, 40,
164, T.), had the following composition : —

Terjjcnes, prmcipaUy ochnene . . 10-0 per cent.

Phenols (eugenol) . . _ . • 55-0

Phenol ethers (as methyl-chavicol) . 5-6

Alcohols (linalol 1) ... . 13-0

Esters as linalyl acetate . . .0-6

Undetermined . . . . .9-8

The fruits of 'Ocinium Aniericanum, from South Africa, were
distilled, and the oil examined at the Imperial Institute {Bxilleiin,
vol. xxii., 3, 1924). It had a specific gravity 0-953 ; optical
rotation, -|- 2-75° ; and refractive index, 1-5110 at 24°.

Goulding and PeUy {Bull. Imp. Inst., 1908, vi., 209) have
examined the oil from Ocinium viricle, distilled in Sierra Beone.
It had a specific gravity 0-911, and optical rotation + 1° 30'.

PERFUMERY

It contained from 32 to 65 per cent, of thymol, 30 to 40 per cent,
of alcohols, and a small amount of esters and terpenes.

Glichitch {Bull. Soc. GMm., 1923, iv., 33, 1536) reports on two
oils from Ocimum viride, one distilled in Grasse, and the other in
New Caledonia. The Grasse oil, which was obtained to the extent
of 2-588 per cent,, was a golden-yellow oil having an odour of
thymol. It had a specific gravity 0-9104 ; refractive index, 1-4962
at 22° ; optical rotation, + 0-9° ; esters, 1-96 per cent. ; total
alcohols, 32-53 per cent. ; and phenols, 38 per cent.

The oil from New Caledonia had a specific gravity 0-9235 at
25-5° ; refractive index, 1-4945 at 22° ; optical rotation, -j- 1-5° ;
esters, 0-73 per cent. ; total alcohols, 26-34 per cent. ; and
phenols, 18 per cent.

Roure-Berirand Fils {Bulletin, October, 1912, 71) have examined
two samples of oil of basil from Mayotte. The odour of these oils
was good ; it recalls, besides that of estragol, a somewhat distinct
odour of anethol. They appear to have been prepared under
favourable conditions. The first of these samples was of brownish
colour ; the second was almost colourless.

Their characters were as foUow : —

Specific gravity at 15° C. .

0-9677

0-9630

Optica] rotation

+ 0° 58'

+ 0° 56'

Solubilit}'’ in 80 per cent,
alcohol

3 vols. and over.

3’2 vols. and over.

Acid value

1-4

0-7

Saponification value

5-6

6-3

Esters (as linalyl acetate) .

1-9 per cent.

2-2 per cent.

These oils differ from the oils of basil of Grasse or Bourbon in
their dea^iro-rotation and their high specific gravity.

The so-called holy basil is Ocimum sanctum. It is common in
India, where it is known as Tulsi or Tulasi. It is venerated by the
Hindus, as the vervain was amongst the Homans. The worship
of the plant is expounded in a book entitled “ Tulaskiava 9 am,”
which contains a hymn in honour of the plant. The oil from the
leaves has been examined by Bacon {Philippine Journal of Science,
1910, 5, 261), and found to have a specific gravity 0-952 at 30°,
and refractive index 1-5070. It contains methyl-chavicol, cineol,
and linalol. Ocimum pilosum is an Indian plant known as Bdbooi-

PEB F U M E B }*

in Bengal and tlic ncighbonrlioocl. Bliaduri {Jour. Ainer.
Ch-cm. Foe.. 1!U J, 36, 1772) has examined the oil distilled from the
whole herb. It is a pale yellow oil containing limonene, citral,
citronellal, cineol, and thj’inol, but no meth 3 d-chavicol. Its
specific gravit}' is 0'SS7 at 25''; optical- rotation, — 3'7° ; and
refractive index, 1-4840 at 25°.

Ocivnnn imnivnnn, the dwarf basil, yields an oil containing
about 14 per cent, of eugenol, and probably linalol. Its specific
gravity is from O-SOO to 0-910 ; optical rotation, — 11° to — 14° ;
and ester value about 12.

BATH SALTS. — Bath salts, or bath cr 3 ^stals, are practically
invariably composed of sodium carbonate, with, occasionallj^, the
addition of a little borax. The use of bath salts does, in fact,
soften hard water in which much lime exists, but the}’’ are
actualh’ used rather as an attractive vehicle for perfume in the
bath. Sodium carbonate, NaoCOg -h lOHoO, in crj’stals of size
according to taste, is the base of nearly all bath salts, the fine
cr 3 \stalline so-called sodium sesquicarbonate being rarely obtain-
able to-da 3 \ They are usuall}’’ tinted with a coal-tar colour,
generall}’’ basic colours, which are spra 3 ’ed in solution on the
crystals, or the carbonate may be immersed in an alcoholic solution
of the d 3 ’e, drained, and dried. In perfuming the cr 3 "stals, per-
fumes should be chosen which are not affected b}’’ alkalies, as
otherwise a more or less speedy decomposition of the perfume ■will
take place. As sodium carbonate is liable to effloresce, a little
glycerine is often added to the crystals to counteract this tendenc 3 ^
Bath powders and water softeners are usually merel}’’ powdered
dried sodium carbonate, with or without a little borax, coloured
and perfumed to taste. A little perborate of sodium is sometimes
added.

BATTEUSE. — ^This is the name given to a machine, in
France, used for beating up a pomade or concrete with alcohol
to prepare an alcoholic solution of their odorous substances, either
for a finished product such as a “ triple extract,” or for further
conversion into an “ absolute.”

BAY, OIL OF. — Bay leaves, from which the West Indian
bay oil is distilled, are, principally, the leaves of Pivicnta acris
{Mtjrcia acris), but no doubt other closely allied species are from
time to time mixed with them. The tree is a handsome one,
growing to the height of 20 to 40 feet, of pyramidal form. In the
woods of Antigua, Janiaica, and Barbadoes the fragrance of these

P E i? E U 31 E n Y

trees permeates tlie atmosphere, so poAverful. is the odom’ of the
essential oil contained in the leaves. The leaves yield from 1 to
1*0 per cent, of essential oil, which contams constituents of such
difl'ercnt specific gravities that the oil is often collected in liglit
and heavy fractions in such an erratic mamier that the com-
mercial oil is frequently nothing more than a fractionated oil of
varying richness in phenols — ^the characteristic odour hearers of
the oil. Tliis has caused a determined effort on the part of the
authorities to place the industry on a sound basis, and to ensure
the manufactm’e of an oil of comparatively constant composition.
These experiments commenced in 1908, and Su’ Francis Watts,
the Commissioner of Agriculture for the West Indies, states that
the results obtained from the experimental plot then established
showed that the cultivation of the tree was a matter worthj^ of
the attention of inhabitants of the islands having uncultivated
land at their disposal. Trees were planted in 1908, and distillation
commenced in 1911, the leaves jdelding practically 1 per cent, of
oil. By 1913 the actual yield of leaves had nearly doubled, and
these also jdelded a higher percentage of essential oil. He also
states that experiments in Montserrat and Antigua show that the
specific gravity and phenol content of the essential oil are
influenced considerabl}'^ by the character of the leaves collected
for distillation, especiaUj^ as the use of immature leaves lessens
the amount and value of the oil.

Assuming that the distillation has been carried on satisfactorily
and the whole of the oil obtained has been bulked, a normal West
Indian bay oil has the following characters : specific gravity, 0-9 65
to 0'98o ; optical rotation, — 0° 30' to — 4° ; refractive index,
1-5100 to 1-5250 ; and phenol content from 55 to 70 per cent.
But if the oil is not so distilled, very different results will be
obtained. To indicate the differences so obtainable, 150 lb. of
leaves were distilled in the Government laboratory at Antigua,
and the oil coming over at intervals of about an hour each was
examined, •odth the following results ; —

Hoxirs.

Specific

gravity.

Phenol content.
Per cent.

1 .

. 0-8669

2 .

. 0-9241

3 .

. 1-0259

4 .

. 1-0381

5 .

. 1-0409

6 .

. 1-0432

n .

. 1-0434

9 .

. 1-0436

7 «

PEBFU MERY

The oil obtained in the first hour amounted to nearly half of
the whole quantity.

The unsatisfactory variations in the commercial oil, which have
not 3^et disappeared, are explained in the account given by
Professor Maiicoe [Pliarm. Jour., [3] viii., 1005), who thus describes
the process : “ The apparatus used in distilling the oil was a
200-gallon copper still heated by steam, so arranged that either
wet or dry steam could be used at pleasure. From 200 to 300 lb.
of leaves vrere used at each running of the still, and to work off
tills quantity required from eight to twelve hours, during which
time from SO to 100 gallons of distillate would be obtained. The
oil comes over in two portions. Fh'st, a portion lighter than
water, that comes over veiy rapidly, and then the heavy oil, that
comes over veiy slowly and does not easity separate from the
water, vdth which it forms a milk}’’ emulsion. The following
notes were made of one of the runs with 200 lb. of leaves. The
distillate was collected in quantities of 2-1 gallons of the water
carefully separated from each portion. The light oil came over in
the first 15 gallons of distillate, from which it promptly separated,
leaving the water quite clear. The specific gravity of each of the
six portions was as follows : 0-870, 0-930, 0-94C, 0-9G4, 0-982,
0-990. The distillation was then continued to obtain the heavy
oil until 65 gallons more of distillate were obtained. This oil was
received in three portions, and the specific gravity of each portion
then taken : 1-023, 1-035 and 1-037.”

An oH of bay distilled in Fiji has been examined at the Imperial
Institute and found to contain only 23 per cent, of phenols, in
spite of a specific gravity 0-961, but to bo ver}’- rich in phenol
methyl -ethers.

Oil of bay contains pinene, and probably dipentene, together
with its principal constituent, eugenol, and its methyl ether.
Chavicol, methyl-chavicol and citral are also present. Power
and Kleber do not agree that pinene and dipentene are present,
but consider the only terpene in the oil to be phellandi-ene. These
chemists also detected a small quantity of the olefinic terpene,
myreene, in the oil.

The odour of the oil is typically phenolic, but differs from that
of oil of cloves or oil of pimento on account of the presence of its
subsidiary constituents.

West Indian bay oil forms the basic perfume for bay rum {q.v.).

The Californian bay is an entirely different tree from that
described above. It is Umhelhilarirt CaJiforuiccf., often known as

PERF U MEB.Y

the mountain laurel or the Cahfornian oHve. This tree has

ighly odorous leaves, which yield an'essential oil which, according
to ;^wer and Lees, contains as its principal constituent a ketone,
C 10 H 14 O, which they have named umbellulone. The oh contains
a small quantity of eugenol, 20 per cent, of cineol, and 10 per cent,
of eugenol methyl ether. It has a specific gravity 0-950, optical
rotation - 3G°, and refractive index 1-4833.

MAYBERRY. ^The hayberr}’-, candleberry, or wax mju-tle of
JNorthern America is Myrica cerifera, a branching shrub of 4 to
8 feet m height. It yields a fragrant essential oil having a specific
gravity about 0-917, optical rotation — 1 ° 30', and refractive
index 1-4990. It resembles the oil from the leaves of the bog
myi-tle (q.y.). The berries also jdeld a wax of considerable value,
and practically identical with bog myrtle wax. It burns in candle
form, vdth a very white flame with very little smoke, and gives
off a very agreeable odour. There are several alhed species of
Ihjnca indigenous to South Africa, which yield a myrtle wax.

BAY RUM. Bay rum is a very highty esteemed toilet pre-
paration, used in general as a hair wash or as a lotion spra 3 ^ed on
the face after shaving. The preparation was originally sent from
the West Indies to this country, and this imported article was
liigWy esteemed. It is probable that it was originally a distillate
of rum Tidth the bay leaves, but Jater a mixture of bay, pimento
and cloves was used. To-day very little bay rum is imported,
as every perfumer manufactures his ovm according to liis own
private formula. The use of rum as the solvent has now almost
entirely disappeared, and the best bay rum is now made from
alcohol and the various essential oils containing eugenol, bay oil,
of course, predominating. Terpeneless oils have been recom-
mended for this pm-pose, and may effect a slight economy in
alcohol, but as most of the oils concerned — ba 3 ^, pimento, cloves,
and cinnamon leaf— are very rich in phenols, the use of the
terpeneless oils is probabl 3 ^ more expensive than filtering off the
small quantity of insoluble constituents.

Cheap bay rum is made with meth 3 dated spirit, fm-ther de-
natured by the addition of extract of quassia. This must not be
done, however, without the permission of the Customs authorities.

suggestion of the presence of rum is sometimes given by the
addition of an artificial essence of rum. This is, in its best
varieties, a mixture based on an impure eth 3 d acetate made from
crude p 3 T’ofigneous acid.

PERFUMERY

BDELLIUM is a somewliat aromatic rcsin which has a resem-
blance to myrrh, and is often found in admixture with it. It
occurs as African bdellium and East Indian bdellium. It is the
product of various species of CommiphoTa and Balsamodendron.
It can be distinguished from m3rrrh by its not yielding the
characteristic reaction with nitric acid. This reaction is as
follows. The gum resin is extracted with ether and the ether
evaporated. The residue is brought into contact with the fumes
of nitric acid. Genuine myrrh gives a violet colour, which is not
the case with bdellium.

Bdellium contains about 75 per cent, of resin soluble in alcohol.
The following figures for bdellium are due to Dieterich ; —

Acid value.

Ester value.

African

12*8

14*4

69*3

9*7

96*4

11*9

95*6

19*2

90*7

J J

20*8

90*1

Indian .

35*7

46*8

3> •

37*2

48*5

(See also under “ Incense.”)

BEESWAX. — ^Beeswax is used by the perfumer in the manu-
facture of cold creams and similar preparations. Natural or
yellow beeswax, the Gei'a flava of pharmacy, is the substance
secreted by the hive bee, Apis melUfica, and probably other
species, to build up the skeleton of the honeycomb. After the
honey has been extracted, the wax is melted with water, separated,
and strained. Beeswax varies from pale yellow to deep brown in
colour, this feature depending largely on the food of the bees.
It is hard, solid, not very unctuous to the touch, and breaks "with
a dull granular fracture. It has an agreeable honey-hlie odour.

The natural beeswax is bleached to a clean white coloirr, either
by exposing it in thin layers to the action of air, moisture and
sunlight, or by treating it with chemicals such as dilute chromic
acid. Chemically-bleached beeswax is more brittle ^an air-
bleached wax, and retains traces of acid, which renders it rather
less desirable for perfumery purposes than the air-bleached variety.
Pure beeswax should have the following characters : specific
gravity at 15°, from 0*958 to 0*968 ; melting point, 61° to 64° ;
refractive index at 80°, from 1*4380 to 1*4420 ; acid value, 16*5
to 22*5 ; ester value, 68 to 78 ; and saponification value, 85 to

PERFU MBB. Y

100. Chemically-bleached wax may have a slightly higher acid
value than that given above.

The principal adulterant of beeswax is ceresine or paraffin wax,
which are far less expensive. Sometimes stearic acid and carnauba
wax are used as adulterants, though this is but rarely the case
to-day.

BELLARY LEAF OIL. — The leaves of Litsea. zeylanica
yield about 0-6 per cent, of an odorous essential oil of specific
gravity 0-890 ; optical rotation, -f 1-5° ; and ester value, 15.
It is an Indian essential oil, which has not, so far, been produced
on a commercial scale for perfumery purposes. It probably
contains geraniol (P. db E. 0. R., 1923, 14, 271).

BENZALDEHYDE. — Benzaldehyde, CgHg.COH, is the essen-
tial principle of the oils of almond, peach and apricot kernels.
These oils contain little else but benzaldehyde, so that the
artificially prepared substance is very commonly used in place of
the natural essential oils. It is a highly refractive liquid, of
specific gravity 1-052 ; refractive index, 1-5450 ; and boiling
point, 180°. It rapidly oxidises to benzoic acid, so that it should
be kept from exposure to air and moisture. The usual starting
point in the manufacture of benzaldeh 3 ^de is the coal-tar hj^dro-
carbon, toluene, which must be separated from accompanj’^ing
impurities before it can be used for this purpose. It is heated,
preferably in a briUiant sunlight, to boiling point, and a current
of chlorine gas is passed through it until it has absorbed 40 per
cent, of its weight. The benzal chloride CgHg.CH.Cl 2 so formed
is mixed with three times its weight of water and its own weight
of powdered challc, and the mixture heated for four hours to
130° C. The mixture is then steam-distilled and the crude benz-
aldehyde purified by conversion into its crystalline bisulphite
compound (see “Aldehydes, Determination of”), wliich is
rendered allcaline, and the liberated benzaldehyde steam-distiUed.

Benzaldehyde so manufactured is invariably contaminated
with organic chlorine substitution products. This fact renders it
of little value if used for perfuming pale-coloured substances such
as white soap, as products perfumed with it steadily darken in
colour. Hence it becomes necessary either to eliminate such
chlorine compounds or to manufacture a benzaldehyde free from
chlorine by a process in which no chlorine is used. The following
are examples of such methods. Three hundred kilograms of
toluene are mixed vdth 700 kg. of 65 per cent, sulphuric acid and

PERFUMERY

well agitated, udtli the gradual addition of 90 kg. of finelj’- powdered
manganese dioxide, keeping the temperature at about 40°. Or
300 Ivg. of toluene are mixed with 150 kg. of oxide of nickel and
heated to 100° for six hours, by which a direct oxidation of the
toluene takes place.

Chlorine-free benzaldeh 3 'de is used as an adulterant of essential
oil of almonds, but as mo.st samples of the so-called chlorine-free
substance contain minute quantities of chlorine (which is not
harmful for anj^ perfumery purpose), the detection of these traces
of chlorine becomes imirortant, as there is a considerable diver-
gence between the jrrices of the natural and the artificial products.
Tire following simple method will detect chlorine when present
in appreciable amount. A piece of filter paper about 2 inches by
1 inch is rolled in the shape of a spill and saturated vdth the liquid.
The paper is placed in a small porcelain dish, which stands in a
larger dish, so that a glass beaker can be inverted over the smaller
dish whilst resting in the larger one. The paper is set alight and
the beaker, moistened with distilled water, inverted over it. When
the flame is extinguished, the inside of the beaker is rinsed out
with distilled water into the outer dish, the liquid, filtered and
tested vith silver nitrate for chlorides. A turbidity or precipitate
indicates the presence of an appreciable amount of chlorine. For
the detection of veiy minute quantities Salamon recommends the
following process. About 2 grams of the benzaldelyde are heated
in a retort with 40 c.c. of concentrated sulphmic acid, and 5 c.c.
of nitric acid in a small retort, and the fumes collected in a solution
of silver nitrate until no fru4;her precipitate is obtained. The
liquid is heated with dilute nitric acid, and the precipitated silver
chloride separated and weighed. Tliis method will detect as
little as 0-01 per cent, of chlorine. Voigt {Z. Angew. Cliem., 1922,
35, 654) has described a combustion method wliich is tedious, but
gives accurate results.

BENZOIC ACID. — ^This acid, CgHs.COOH, is the simplest
acid of the aromatic series. It is found to a small extent in the
free condition, but principally in the form of esters {vide “ Ben-
zoin ”). It is a crystalline substance melting at 121°, and having
a slightly aromatic odom’ suggestive of vanilla. To obtain it
fr6m benzoin the dry powdered gum is placed in a metal receptacle,
covered with a filter paper pierced with pin holes, and covered
with a paper hood. The powder is heated, and the benzoic acid
sublimes and collects on the paper hood. It is prepared on a
considerable scale artificially by the hydrolysis of the chlorination
r- 81 6

P E F U 21 E RJ

product of toluene. It is emplo 3 ^ed largeh* as a preservative of
fats, sucli as lard, etc,

_ BENZOIN.— Benzoin, or Gum Benjamin, as it is often called,
IS an important balsamic resinous material, much used in the
perfumery industry, both on account of. its sweet heavy odour
and Its useful fixative properties. It is used in the manufacture
of incense. The earliest literature dealing with the subject speaks
of benzoin as Lxiban Jawi (“incense of Java”), the name

aya being used for Sumatra and other neighbouring islands.

t IS easy to tiace the modern name through successive corruptions
of the above name: banjavd, benjui, benzoi, benzoin, and
benjamin. There are several types of benzoin, of which Siam
benzom is preferred for perfumery purposes. This is the product
of a tree not 3 ^et identified with certainty, but which may be
Styrax Tonlinense. The trees do not produce the secretion
normaUy ; a wound is inflicted in the bark sufficiently deep to
mjure the cambium, which results in the formation of oleoresin
ducts in which the secretion is produced. It is, in fact, a patho-
logical secretion. When sufficiently hard and dry, the material
is collected, either in the form of lumps or in small tears. The
principal tynstituents of Siam benzoin are free benzoic. acid and
the benzoic ester of the alcohol lubanol. There are also present
siaresm 3 d benzoate, vaniUm, and traces of other aromatic sub-
stances. The combined benzoic acid amounts to about 25 per
cent., and the free benzoic acid to about 15 per cent. It should
jpield 90 per cent, at least of extract to alcohol, and should not
contain more than 2 per cent, of mineral matter.

Beinitzer {Arch. Pharm., 1921, 259, 1 , 60) has isolated a smaU
amount of siaresinolic acid from Siam benzoin. It is a crystalline
substance of the formula C 30 H 48 O 4 , melting at 260°. He also
fuUy examined the ester lubanol benzoate, C 17 H 16 O 4 , which he
found to cr 3 ^stallise in plates melting at 72° to 73 °, Eor further
details the papers above q^uoted should be consulted.

Sumatra benzom is of weaker and less agreeable odour than
Siam benzoin. It is derived from Styrax Benzoin, and owes its
odour principally to the cinnamic acid esters of benzoresinol and
benzoresinotannol. There are also present free benzoic acid,

st 3 nol, benzaldehyde, vanillin, phenyl-propyl cinnamate, and
styracin.

Other varieties are those -known as Balambang, Padang and
Penang, but they are not used in ‘ perfumery except for the
manufacture of incense.

PERFUMERY

Siam benzoin is esteemed b}' perfmners on account of its
vanilia-like odom'. A full and interesting account of the history
of benzoin by E. IM. Holmes -vdll be found in the Perfuviery and
E-sscnfial Oil Record, 1916, 112, in which he gives the following
details in regard to Siam benzoin, the method of collection being
described in the Keio Bulletin, 1895, 195 ; —

The season for collecting the benzoin is in July or August,
when the work in the paddy fields is finished, till November.
The trees arc notched with an axe, and the exuded soft resin is
allowed to remain on the trees for three months to harden, so that
the benzoin is read}' for sale in December.

It is sorted into tluee classes. The best, or “ Sua,” is in large
lumps, and is clean ; the second consists of smaller lumps, and
has some bark attached to it, and is half the value of the first ;
the third, or “ Musi,” is soiled with dust and dirt, and is in fine
small pieces. It is collected by the Siamese Thai, Annamites, and
Tongoos, who have settled in the province and carried on the
work from time immemorial. This account is furnished by
Siamese, not Eiuopean, observers.

In 1910 an apotheker at Basle, Herr Hartman Rordorf, published
an interesting account of the collection and preparation of Siam
benzoin in the SchweizeriscJie WoJienscJirift, having fortunately
been able to obtain information through his brother-in-law, Dr.
Domeller Nieuwenhuis, the Dutch Minister in Siam, who lived
some j’^ears in Bangkok. Great difficulty was experienced in
obtaining information and specimens. Between 1907 and June,
1910, ten expeditions were sent to obtain material, but all except
the last proved imsuccessful. The road and paths in northern
Siam are very bad, and the commercial traffic is chiefly carried
by the rivers. At high water these are not navigable, and at low
water are impassable swamps. The morasses are navigable only
for a short period during the year. The period necessary to
traverse them is three days before the benzoin-producing region
can be reached. In this neglected district there is a settlement
of small, long-haired people who collect the benzoin, and who
apparently emigrated from China in very early. times. They speak
an old forgotten language and wear different clothes from the
natives of southern Siam.

This method of coUecting the benzoin and preparing it for
market is as follows : On trunks of 20 to 25 cm. in diameter, pieces
of bark of rectangular shape from J to 4 handbreadths in size are
loosened, and the resin runs out on the inner side of the bark,

C — 2

PETIT U 31 E P I

solidifying there Ijy the heat of tlie snn. This forms the finest
qualit.y. Tlie smaller fragments are formed into lumps by hand.
The resin is spread out on a strong mat in a heap, and gmger roots,
first hollowed and filled with the marrow of the bone of the pig,
are mixed uith it, and the mats are tied up at the ends into a
bundle. The contents are examined from time to time to see
if the fat has been taken up, and if not, fresh fat is^ used. It is
-^aid that rancid fat uiU not, lilce fresh fat, pass through the ginger
root. The process takes about a year, its object being to preserve
a fine aroma. When the fat has disappeared from the ginger the
drug is ready for export vithout risk of losing its fine odour
through the long hot joirmey to Bangkok. The natives rub the
gum resin with sugar and then make it uito an emulsion with
^'-•ater. vrliich is highly prized as a wash and as an addition to
baths. The specimen of Siam benzoin in the museum of the
Pharmaceutical Society obtained from vdiolesale commerce in
this country iDears out this description fairly well. In some
specimens large tears of benzoin are attached to the inner .smlace
of a moderately thick bark, and differ from the Sumatra land not
only in the vanilla odour, but in the fact that the tears are
unusually free from one another. It seems quite possible that
this is due to their having an oily surface, caused bj’- the hog’s
marrow, which would probabty prevent loss of benzoic esters to
some extent and thus conserve the natm’al fragrance of the resin.
It is interesting to record that Herr Hordorf has found resin canals
to be abundantly present on the inner surface of the bark {Pliarm.
Jour. (4), 31, 515).

The most recent contribution to the knowledge of the tree
yielding Siam benzoin was published in 1913 in the Axiothelcer
Zcihing, by Dr. C. Hartwich, who received specimens of the
matiure fruit as well as leaves, bark and resm from Messrs. Bilder-
meister and Schoch Bilhviller from San Hua, which is nearly in
the centre of the Siam benzoin district, between Luang Phrabang
and Hanoi.

Dr. Hartwich beheves that the produce of this district passes
through the tovui of Luang Prabang into Siam, since Thorel
reported in 1866 that the benzoin was collected on the mountains
between Laos and Tonldn, in latitude 19 N., in the forests of one
of the affluents of the east of the Mekong River on the frontier
of Armam. The sample of Siam benzoin received by Dr. Hartwich
was white internal^ and brownish externally, and 3delded no
cinnamic acid, and the fruits were oval, as might have been

.84

PEBFU ME BY

expected from Tliorel’s herbarium s25ecimens above mentioned.
The mature fruits were submitted to the Ro 3 ’-al Gardens at Kew
for identification, and vere there determined by Mr. Craib to be
identical with the Anihoslyrax Tonldnense of Pien'e and the Styrax
rnacrotliyrsus of Perkin.

B_v the rules of priority*, Perkin's name comes first, but as
Anihoslyrax is regarded at Kev as a sub-genus onlj’-, IMi-. Craib
has named the tree Styrax Tonldnense. The fruit is elliptical,
smootli, vith a thin pericarji dehiscing longitudinally into three
valves, and an ellijDtical, oval, dark brown seed, which is rough
with minute papillae. It is thus quite different from the fruit of
S. Benzoin, which is globular, nearly an inch in diameter, with a
thick pcricaiq), which is indehiscent.

Another sjeecies of Styrax, S. henzoicles, Craib, is rejeorted to
j'ield benzoin near Chieng-mai, in Siam, but the resin does not
possess the same apjeearance as the Siam benzoin of commerce,
and is probabl,y onlj" used locall 3 \ It ma 3 ’- therefore be con-
sidered proven that Styrax Tonldnense is the botanical source of
Siam benzoin.

The following are average figures for benzoin of good qualit 3 ’-,
free from admixture with earth 3 ’’ matter, etc. : —

j Sinni.

I Sumatra.

Other varieties.

' Under 2 per cent.
Soluble in 90 per i

1 Under 2 per cent.

Under 3 per cent.

cent, alcohol . '90-96

1 90-94

'85-95

Acid number . j 130-15S

1 98-140

106-142

Ester number . ' 42-69

1 I

50-100

50-90

Cocking and Kettle, in a paper read before the British Pharma-
ceutical conference at Chester in 1914, gave the following com-
plete anal 3 \ses of eleven samples of Sumatra and Siam benzoin
(see p. 86).

If Sumatra benzoin be warmed with chromic acid mixtime, a
strong odour of benzaldehyde is given off, owing to the oxidation
of cinnamic acid. This distinguishes it from Siam benzom.
According to Muter, Siam benzoin gives the following character-
istic reaction. If the dried petroleum ether extract of the resin is
treated with sulphuric acid, a cherry red colour is developed. It
is frequently of importance to determine the amount of benzoic
acid in benzoin. This can be done b 3 '^ digesting 10 parts of the

PE11FVMER7

takablo odour of beiizaldehyde was produced.

PERFU M FRY

powdered gum with 6 parts of slaked lime and 100 parts of water.
After sis hours the liquid is boiled, filtered, and the residue
washed. The filtrate is concentrated, acidified with hydrochloric
acid, and well cooled. The precipitated benzoic acid is filtered
off, washed with a little water, and dried between porous paper.
The small amount of benzoic acid left in the mother liquor is
extracted with chloroform and dried in a desiccator and weighed.
To estimate the total balsamic acids, Cocking and Kettle give the
follovdng process : Five grams are extracted, with alcohol in a
Soxhlet tube and the extract hydrolysed with alcoholic potash.
The alcohol is evaporated, the residue dissolved in 100 c.c. of
water and rendered faintly acid with hydrochloric acid, and then
6 grams of magnesia and 20 c.c. of xylene added. The whole is
boiled under a reflux' condenser for an hour, cooled, the aqueous
liquid filtered off, and the insoluble matter boiled twice with
100 c.c. of water, which is allowed to cool before being filtered.
The combined aqueous extracts are extracted once with ether,
then acidified with hydrochloric acid, and the liberated balsamic
acids shaken out with ether. The ether is evaporated and the
residue dried in vacuo over sulphuric acid and weighed.

In the manufacture of incense powdered benzoin always plays
an important part (see " Incense ”). There is also a plant known
as Benzoin odoriferum {Laurus henzoin), commonly termed spice
wood or wild allspice, which grows in various parts of North
America. Nearly every part of the plant yields an aromatic oil,
that from the bark probably containing cinnamic compounds.

BENZOPHENONE. — Benzophenone, or diphenjd ketone
CeHg.CO.CoHg, is a fragrant crystalline body, melting at 48°
and boiling at 307°. Its specific gravity at 50° is 1-098. It is
prepared by distilling calcium benzoate or by the condensation
of benzene with benzoyl chloride in the presence of- aluminium
chloride. It is useful in the preparation of heavy odoms of the
so-called Oriental type.

BENZOYL ISOEUGENOL. — ^This body is a substituted
isoeugenol of the formula C6H5.CH2.(C9 H:i 202). It forms small
crystals melting at 59°, and has a slight odour. Its principal value,
however, lies in its use as a fixative. It is recommended in the
fixation of carnation, fern, rose and orchid perfumes.

- BENZYL ACETATE. — ^Benzyl acetate is an ester of the
formula CcHg.OHa.O.OC.CHg. It occurs naturally in oil of jasmin,

PERFUMERY

oil of 3 'ltmg-ylangj oil of tuberose, and similar flower oils. Its
odour is sweet, but not intense ; it is prepared synthetic allj’', and
is indispensable in the preparation of artificial flower oils of the
jasmin or ylang- 3 dang ty^pes. It is a colourless oil, soluble in anj''
proportion in 90 per cent, alcohol. Its specific gra^vity is about
1-000 ; refractive index, 1-5034; and boiling point, 216°. It
may be prepared by boihng for thirty hours a mixture of 5 parts
of benz^d chloride, 4 parts of fused sodium acetate, and 4 parts
of a glacial acetic acid. Excess of acetic acid is removed by
distillation, and the ester is washed and rectified. It should be
free from chlorine, as specimens containing more than faint traces
tend to discolour soap, etc., which has been perfumed by this
substance.

BENZYL ALCOHOL.— This body is the lowest member of
the normal aromatic alcohols containing the benzene nucleus,

It has the formula CgHj-CHoOH. It exists in the free state to a _
small extent in those oils which contain its esters, such as jasmin,
tuberose, cassie flowers, jdang-jdang, etc. It is useful in the
preparation of such artificial flower oils. It is an oil of specific
gravity about 1-04S ; refractive index, 1-5400 ; and boiling
point, 205° to 207°.

It is useful to the perfumer not onty for its slight floral odour,
but as a fixative, and also as a solvent for artificial musk.

It maj’’ be prepared bj’’ mixing magnesium h 3 ^drate (1 molecule)
with benz 3 d chloride (2-2 molecules) and adding about ten times
the weight' of water. The mixture is maintained at 100° for some
hours with continual shaking. The 3 deld is about 95 per cent, of
the theoretical.

BENZYL BENZOATE.— This ester, of the formula
CpHg.COO CHa.CgHg, occurs naturallvj n balsam of Per u, and to
a small extent in 3 dang- 3 dang, tuberose, and similar flower oils.

It is, when quite pure, a ciystalliue solid meltmg at 21°. In
commerce, however, the artificial ester contains minute quantities
of unobjectionable impurities, which keep it hquid at ordinary
temperatures, and the melting point seldom exceeds 18° to 19°.

It has a specific gravit 3 ’' 1-1224, refractive index 1-5685, and boils
at 323°. Its odour is very slight, but strong enough to be of
value in reproducing floral odours. It is also a very useful fixative,
and an excellent solvent for artificial musk. It should be free
from chlorine. It is obtained commercially b3’' dissolving sodiuin
in benzyl alcohol and heating it with benzaldeh 3 ’-de for twent 3 ^

PERFUMER 7

four liours on a water bath. The mixture is acidified mth acetic
acid, and the ester precipitated by water and rectified.

BENZYL BUTYRATE. — Benzyl butjwate is an ester which
has a softer odour than benzyl acetate, and is indisj)ensab]e in
correcting the harshness of the latter in the best artificial jasmin
perfumes. Its formula is CgHg.CHg.OOC.lCgH-). It has a
specific gravity l-Olo, refractive index 1'4945, and boils at 242°.

BENZYL CINNAMATE. — The cinnamic ester of benz 3 d
alcohol, of the formula CgHj.CHo.COO.CH : CH.CqHj, is found
as a natural constituent of storax, balsam of Peru, and balsam
of tolu. It is a cr 5 'stalline substance with a characteristic sweet
balsamic odour. It is prepared artificially bj^ heating sodium
cinnamate, alcohol and benzjd chloride under a reflux condenser.
It forms white crystals melting at about 32°. It boils at 195° to
200°. It is used in the preparation of heavy odours of the Oriental
type, and is also useful as a fixative.

BENZYL CYANIDE.— This compound, CgHs.CHsCN, is a
natural constituent of oil of neroli and of certain cress oils. It is
a liquid of powerful odour, boifing at 231° and having a specific
gravity 1-016. It is probablj’' an intermediate substance in the
formation of phenjd-acetic acid in plants in which this acid occurs.
It is an imj)ortant intermediate in the preparation of synthetic
phenyl-acetic acid, and can be prepared b 5 '- the action of sodium
cj’-anide on benzjd chloride.

BENZYL-ETHYL OXIDE.— This oxide, of the formula
OgHjCHo.O.CoHg, is a colourless oil, useful in perfuming soap on
account of its resistance to alkafies. It has a penetrating fruity
odour.

BENZYL FORMATE is an oil havmg an odom of jasmin.
It is somewhat harsh in odour, and should be used in small
quantities only. It maj’’ be prepared b 3 ’' the action of formic acid
on acetic anh 3 ’’di’ide, and then esterifying benz 3 d alcohol vdth the
mixed anliydride so formed. Benz 3 d formate boils at about 202°,
and has a specific gravity 1-083, and refractive index 1-5195.

BENZYL - HEPTINE - CARBONATE.— Fide Heptine-

carbonates.”

BENZYL-METHYL-CARBINOL.— This body is a fragrant
oil, isomeric ^vith phenyl-propyl alcohol. It boils at 215°, and has
the formula CcH 5 .CH„.CH( 0 H)-CF 3 .

PERFU M EB Y

BENZYL PROPIONATE. — Like the coiTesi3onding loutyrate,
this ester has a softer and sweeter odour than the acetate,
and is used to correct the harshness of the latter in artificial
jasmin odours. It has the formula CcH6.CH2.00C(C2H5). It has
a specific gravity about 1-0362 ; refractive index, 1-4980 ; and
boiling point, 228°.

BENZYL SUCCINATE. — This substance, of the formula
(CgHg. 0112)2(000)2(0112)0, is a crystalline odourless powder
meltmg at 45°. It is a useful fixative.

BENZYL VALERIANATE. — This ester, of the formula
OeH5.0H2.000.(04H9), is prepared by esterifjdng benzyl alcohol
vith valerianic acid. It has an odour of valerian, and is used in
minute quantities in a number of floral oils, such as artificial otto
of rose. Its specific gra^nty is 0-996 ; refractive index, 1-4880 ;
and boiling point, 250°.

BENZYLIDENE-ACETONE.— This ketone, OgHg.OH.-OH.

OO.OII3, ^ sweet floral odour. It is used to round off and
modify artificial flower oils, but is especiaUy useful as a basic
material for artificial sweet pea perfume. It is a crj^stalline body
of specific gravity 1-0377, melting at 42°, and boiling at 260° to
262°. It is prepared by mixing 22-5 kg. of acetone, 15 kg. of
water, and 15 kg. of benzaldehyde. The mixture is cooled to 10°,
and 9 kg. of 10 per cent, solution of caustic soda is slowly added,
with constant stirring, care being taken that the temperatiu’e does
not rise materially. The excess of acetone is removed by distilla-
tion, and acetic acid added. The ketone is then steam distilled.
According to Lewinsohn (P. dh E. 0. B., 1924, 118), a distinct
improvement of the yield obtained by these methods results if
allowance is made for the fact that -water is produced to the
extent of 16 per cent, of the benzaldehj^de reaction mixture, this
water causing dilution of the soda lye. The strength of the
10 per cent, caustic soda solution can be maintained by the
gradual addition of a 20 per cent, solution so as to counteract
the dilution caused by the water produced in the reaction.

The method of conducting the operation is as follows. In a
jacketed mixing vessel of iron — ^provided with means for heating
and cooling by passing steam or water through the jacket— are
mixed 22-5 kg. of acetone and 15 kg. of benzaldehyde. The
mixture is cooled to about 10°, and 8-7 kg. of 10 per cent, caustic
soda solution are slowly added with vigorous stirring. The
solution becomes lemon yellow in colour. As a result of the

PERFUMERY

reaction, 2-54 kg. of water. are produced, and, in order to maintain
the strength of the solution, ten hourly additions of 250 grams of
20 per cent, caustic soda solution are made, and the mixture is set
aside for two days. At the end of this period 20 kg. of cold water
are added, thus causing the benzylidene-acetone to precipitate as
a brown oU. After wasliing with dilute acetic acid and sodium
carbonate solution, the oil iS distilled under diminished pressure,
a bright yellow oil coming over at 151° to 153° under 25 mm.
Tliis oil possesses a fresh and characteristic odour, and after a
short period, especially if sown with a crystal, the oil solidifies
to a bright yellow crystalline solid melting at 41° to 42° C.

On account of its exceptionally penetrating nature, benzylidene
acetone should be used in perfumery with great caution, and only
as a 10 per cent, solution in alcohol. Its stabfiity to allvali makes
it of special value as a soap perfume. In its concentrated state
benzylidene acetone violentlj’- attacks the skin. M.D.

BERGAMIOL. — This is a name often used for so-called
artificial bergamot oil, consisting principally of linalyl acetate
made from linalol obtained from linaloc or other oils.

BERGAMOT OIL. — This oil is one of exceedingly soft and
sweet odour, and is indispensable m the manufacture of many
perfumes. It finds a prominent place in all formulaj for eau de
Cologne, in many for lavender water, and in a very large number
of other fancy perfumes. It is expressed from the peel of the fruit
of Citrus a^irantnm, sub-species Bergamia, a tree belonging to the
natural order Rutacece. The chief centre of the bergamot industr}^
is southern Calabria, in which district practically the whole of the
supply of bergamot oil is produced. There are extensive planta-
tions in the neighbourhoods of Reggio, Melito, Gallico, S. Lorenzo,
and other districts. The oil is expressed by machines, distilled
oil losing much of its odour and being of little value to the
perfumer. The oil varies in colour from a rich golden brown to
a distinct green, usually the latter. The green colour is due to
the presence of traces of chlorophyll, and not, as is often stated,
to copper. The fruits are gathered during November and
December, and the oil expressed from the peel and packed in
coppers or tins for exportation.

Pure oil of bergamot has the following characters : specific
gravity, from 0-880 to 0-887 ; optical rotation, -f 8° to 22° (rarely,
a little higher) ; and refractive index, 1-4640 to 1-4675. It should
yield from 4-5 to 6-5 per cent, of solid residue when dried

on a

PERFUMER Y

^Ta^er bath. This consists of wax, colouring matter, and other
substances dissolved by the oil from the peel, including bergaptene
{q.v.). The jirincipal odorous constituent is linatyl acetate,
CjoHjy.CO.T.CHT, which is present to the extent of about 38 to
42 per cent. Oils with much less than 38 per eent. are usualty
adulterated, the principal adulterant in such cases being lemon
terpencs. Such adulterated oils are often fortified with artificial
esters to bring up the ester value, in the hope that they will be
regarded b,y the user as natural esters. The presence of many
such artificial esters is revealed b}" the increase in the weight of
the non-volatile residue, and bj^ the high saponification value of
the latter. The normal residue on the water bath has an acid
value about 18 to 30, and an ester value of llo to 180.

If unripe fruits are used for the preparation of the oil, it may
have a sj^ecific gravity domi to 0-S7S or 0-879, and contain less
than 30 per cent, of esters.

During the iwcsent season (1923-1924) the writer has found
undoubtedly authentic samples of bergamot oil having cpiite
abnormal characters. The oils contained only about 35 per cent,
of esters, had a low siDccific gravity — ^from 0-880 to 0-881 — and
contained between G and 7 per eent. of fixed residue. This fixed
residue is normal in character. Ogston and Moore (P. ct E. 0. R.,
1924, 78) have also recorded such .samples, which appear to 'be
due to imperfect ripening of the fruits.

There is a bastard bergamot, known as bergamotella {Nero de
Bergamotio), which is occasional^ mixed with the normal fruit.
In such cases the specific gravity is raised, as the oil from the
bastard fruit often reaches 0-898, and the ester value is reduced
considerably.

Bergamot oil contains, besides linalyl acetate, limonene, pinene,
camphene, bornylene, bisabolene, Zccro-linalol, dihydrocumic
alcohol, nerol, terpineol, and bergaptene.

BERGAPTENE. — This body is the principal constituent of
the residue of oil of bergamot when evaporated on a water bath.
It is present to the extent of about 5 per cent. It has the formula
CjoHgO.!! Eiwd melts at 188°. It is the methyl ether of a phloro-
glucinol derivative allied to coumarin, and is isomeric vdth
xanthotoxine^.

BETA-IONONE.— See “ lonone.”

BETA-NAPHTHOL ETHYL ETHER.— See “ Bromclia. ’

PEl^FU M E li Y

BETEL, OIL OF. — The essential oil of Piper heth (Chavica
hetle) is distilled from the leaves of the plant, one of the Piperaceoi,
Tlie leaves jneld up to 1 per cent, of oil (occasionally higher), vith
a characteristic odour of the plant. It is a heavy, yelloudsh liquid
of specific gravity, usually from 1-020 to 1-050, but sometimes
only about 0-960. Its refractive index is over 1-5000. It contains
methoxy-chavicol (betel phenol) as its principal constituent,
together vitli a little chavicol, a sesquiterpene, and possiblj’- cineol
and cjnnene. Its odour is persistent and typically phenolic.

BETEL PHENOL. — ^This body is identical with chavibetol,
the phenolic constituent of betel oil. {Vide “ Chavibetol.”)

BETULA LENTA, OIL OF. — See “ Birch (Sweet), Oil
of.”

BEU-RIENG, OIL OF. — ^This essential oil is lu-oduced in
certain districts of China, and is probably the product of either
an Alpinia or a Zingiber species, but at present its origin is
uncertain. It has a very pleasant odour, recalling that of an
infusion of tea. Its specific gravity is 0-902 ; optical rotation,
— 8° 8' ; and refractive index, 1-4884. It contains over 30 per
cent, of free alcohols (Gattefosse, La Parfwnerie Moderne, 1922,
109).

BEURRE DE VIOLETTES, — Owing to its pronounced
violet odom-, the concrete oil of orris is frequently Imownmnder
this name.

BIGARADE. — ^This name is applied to the essential oils
derived from the bitter orange fiowers and fruits, e.g., “ oil of
orange bigarade ” and “ oil of neroli bigarade,” in contradistinction
to the corresponding oils from the sweet orange, which are known
as “ oil of orange Portugal ” and “ oil of neroli Portugal.”

BIGNONIA. — Bignonia suaveolens {Sterosperimim snaveo-
lens) is a plant whose flowers possess a most exquisite fragrance,
but - so far facilities do not appear to have allowed any practical
use of them in the perfumery trade. The tree is foiuid tlu’oughout
the nioister parts of India. It is the Pdtald of Sanskrit vwiters,
and is kno\vn as Kama-duti (messenger of love) or Madhu-duti
(messenger of spring). The flowers are very 'beautiful in appear-
ance, and of exquisite perfume. Bees prefer them to any other-
flower, and native poets describe them as the quiver of Kamadeva,
the Indian Cupid (Sir W. Jones, “ Asiatic Researches,” iv., p. 289).

P B P F U M BBT

BIRCH (SWEET), OIL. OF. —The flavotu’ and perfume of
■uintergreen are very highly appreciated, especially in the United
States. As a perfume material, however, the essential oil of
wintergreen is used in this country, not to a great extent for its
ovn odour to predominate, but in small quantities, to modify
other and more pronounced odours. But as the essential oil of
wintergreen is practically identical with the oil distilled from the
bark of Bciula Icnia, the " sweet birch,” true oil of wintergreen
is lo-daj' seen but little in commerce, as sweet bkcli oil can be
obtained at a much lower price. It should therefore be under-
stood that the expression ” oil of wintergreen ” is usually meant
to indicate that the product is either the distillate of the winter-
green leaves {Ganltheria procumhens) or of birch bark {Betula-
hnia). the price indicating whether it be the former or the
latter. But it is to be feared that in most cases it is, in fact,
the distillate of Betula lenia, whatever the price may indicate.
Both oils, however, consist almost entu’ely of the' ester methyl
salicylate {q.v.), so that there is a good deal of fraud in the article,
the cheap artificial ester being very frequently substituted for the
more expensive natiu’al oil. Apart from price considerations, how-
ever, there is j)ractically no difference between oil of wintergreen,
oil of sweet birch, and artificial method sahcylate other than a
slight difference in the delicacy of the odour, in regard to which
the individual perfumer must make his own decision.

The true wintergreen, GauUheria procumleiis, is known also
under the names mountain tea, box berry, spice beny, and ground
holly. It is a small creeping slu’ub found in the southern parts
of Canada and the northern parts of the United States. All parts
of the plant contain essential oil, but the leaves are almost
exclusively used for distillation purposes. The apparatus ui^ed
for distillation is primitive m character, consisting of small
whiskej’- stills or of wooden casks with copper bottoms. The oil
does not exist as such in the plant, but in combination as a
glucoside, gaultherine, which is decomposed on distillation.

The sweet bu’ch {Betula leuta) is a tree which attains a height
of 10 to 25 feet, occasionally growing to a height of 76 feet. It
is found in moist woods from New England westwards to Illinois,
and thence along the Alleghany regions southwards. The best
yield of oil is obtained from the wood cut in the summer months.
The wood is cut into small pieces and allowed to macerate in water ‘
for twelve hours before distillation.

The characters of wintergreen and sweet birch oils are practically

PEBF U MEB Y

identical. The specific gravity varies from MSO to MS7, and
both oils contain from 98-6 to 99-6 per cent, of methyl salicylate.
Power and Kleber {ScMmmeVs Bepori, October, 1895, 50) have
made an exhaustive examiuation of the two oils, and their results
indicate that there are only minute differences between the two
, oils. It is suggested that oil of wintergreen has a very small
optical activit}- — not less than — 0° 25', whilst sweet birch oil
is opticaUj- inactive. This, however, is very doubtful. A sesqui-
terpene alcohol, betulol, C^sHo^O, and its acetic ester have been
identified in sweet birch oil. A test for distinguishing between
the two oils has been suggested bj^- J. C. Umney (P. cO E. 0. B.,
1914, 5, GO). To 5 drops of the oil in a test-tube add 5 drops
of a 5 per eent. alcoholic solution of vanillin and 1 c.c. of alcohol.
Shake well, and add 2 c.c. of concentrated sulphuric acid, and mix
thoroughly. Pure wintergreen oil gives an intense crimson-red
colour, pure sweet birch oil gives a deep blood-red colour, whilst
synthetic methyl salicylate gives a yellow colour.

GaiiliJieria punctata, a plant found in British India and the
Dutch Indies, yields an essential oil practically identical with the
oils described above.

GaultJieria fragrantissima has been experimentally distilled for
“ wintergreen ” oil in Assam, but the ;ydeld has, so far, not been
sufficient for it to be a commercial success.

If the oil is found to contam traces of chlorine (see under

Benzaldehyde), it is certain that it is, or contains, artificial
methyl salicjdate. When of good quality, the artificial ester
should contain at least 99 per cent, of true methyl salicylate. It
has the following characters: specific gravity, 1-182; optical
rotation, 0° ; refractive index, 1-5375 ; and boiling point, 224°.

Artificial cassie oil, new-mown hay, and chypre perfumes
■-usually contain very small quantities of methyl salicylate. It
is also largely emploj^ed as a flavour for chewing gum and for
tooth pastes and powders.'

DIRGH tar oil. — ^T his oil is used to dress certain types of
leather, originally for the purpose of covering objectionable odour,
but to-day rather to impart to the leather the pleasant odour
known as that of “ Russia leather.” It is prepared in Russia by
the destructive distillation of the wood and bark of Betula alba.
The crude tar is redistilled and a brownish oil is obtained, which
is known as rectified birch tar oil. It is a liquid of specific gravity
from. 0-920 to 0-946. It contains over 40 per cent, of phenols,
principally guaiacol, creosol, cresol, and xylenol. The crude oil

P E P F U iV E F Y

has a specific gravity 0-928 to 0-9G0. If a. 5 per cent, solution in
2 octroleuin ether be shaken vitli a 0-1 per cent, aqueous solution
of cojqDer acetate, it should not become green in colour (absence
of fir tar as an adulterant). This oil is known in pharmac}’’ as
OJewn Evsei.

BISABOL MYRRH. — See under “ Myrrh ” and “ Opox^onax."

BISABOLENE. — This body is a sesquiterpene, C 15 H 04 , found
in the essential oil of bisabol myrrh. It is identical v'itli the
hydrocarbon originally discovered in oil of limes by H. E. Burgess,
and named by him limene. It is a colourless oil having a .specific
gravity 0-SSl ; optical rotation, — 41° ; refractive index, 1-4901 ;
and boiling at 112 ° at 4 mm. jiressure. It has an odour of myrrh.

BITTER ALMOND OIL. — See “ Almonds, Oil of.'’

BITTER ORANGE OIL.— See “ Orange, Oil of.”

BLE DES PAGODES.— The essential oil known under this
name is of unknown botanical origin. It emanates from Annam,
and lias been investigated by Roure-Berlrand Fils [Bulletin, April,
1920, 32). It resembles in odour the oils of palmarosa and ginger-
grass, with a definite odour of cummin.

BLUMEA, OILS OF. — The oil from Blumea halsamifera is
an aromatic liquid containing Zccro-borncol, Zcero-camiDhor, a
sesquiterpene, a sesquiterpene alcohol, cineol, limonene, and about
5 per cent, of a ifiienolic compound. It has been examined by
Jonas [Schimmel <0 Co., Bericlit, April, 1909, 149), who found it
to have the following characters : —

Specific gravity . . . 0-950

OiDtical rotation . . . . — 12° 30'

Refractive index . . . 1-4815

Acid value .... 23-4

Ester value .... 1

Ester value after acetylation . 198

The phenolic compound is probably iDliloroglucinol-trimethyl
ether.

Blumea halsamifera is indigenous to India, and is found from
the Himalayas to Singapore, and in the Malay archipelago. It is
also found in the islands Hai-nan and Formosa. In Hai-nan and
IXAvang-tung it is distilled for the production of Ngai camphor,
as it is called, or Nga'i-fen, as the Chinese caU it. This substance
is used for ritualistic purposes, and also for the manufacture of
' 96

PEUFU MERY

so-called “ Chinese inlc,” and in medicine. Ngai camphor is the
loevorotatory variety of borneol,

Simonsen and Ran {Jour. GJiem. Soc., 1922, 876) have examined
the essential oil of Bhmca Malcomii. This is a small herb, known
in Marathi as Panjnil. It occurs in the western part of the Deccan
plateau at elevations of about 2,000 feet. It has a pleasant
camphoraceous odour. The fresh green material yielded about
0'2o per cent, of essential oil, which was found to consist almost
entirely of two ketones, d-carvotanacetone and Z-tetrahj^dro-
carvone. Traces of acids, esters, and a phenol were found.

BOG MYRTLE.— The bog mjTtlc (sweet gale, bastard
myrtle), Myrica gale, has no connection with the true mjTtle.
It is a native of Britain, and is found in France, Holland, northern
Europe, and the United States. It is a small fragrant shrub,
found chiefly in boggy places. Its leaves yield a small quantity
of a fragrant essential oil having a specifle gravity from 0'89S to
0-915 ; optical rotation, — 5° to — 12° ; and ester value, 15 to
25. The principal odour value of the plant, however, lies in the
fact that the fruit consists of a very large quantity of small berries,
which jdeld, on treatment wth hot water, a quantity of wax
which, when used for candle manufacture, gives off a delightful
odour on burning, hlyrtle wax is somewhat variable in colour,
usually of a yellowish green shade.

BOIS DE CITRON.— See under “Bois de Rose” and
“ Linaloe Oil.”

BOIS DE ROSE, OIL OF.— The so-called oil of Bols
Rose must not bo confounded with oil of rosewood {q.v.), which is,
as found in commerce, usually an entirely factitious oil. Oil of
Bois de-Rosc is frequently known as cayenne linaloe oil, and here
again must be distinguished from hlexican linaloe oil, which is
the product of various bursera species. Cayenne linaloe oil, or
oil of Bois de Rose femelle, as it is described in full, has usually
been described as the product of a tree known as Licari Kanali.
The botanical origin of the oil has, however, been very obscure
until B. M. Holmes published the most reliable account of the
matter in 1910 (P. & E. 0. R., 1910, 32). The wood, he states,
has been named by various writers Bois de Citron, Bois de Rose
male, Bois de Rose femelle, Bois de Cedre jaune, etc. According
to Guibort, the name Bois de Citron has been applied to three
distinct woods, namely : (1) that of Amyris balsamifera, now
known to be the tree yielding the West Indian so-oalled sandal-
P. W f

P E P F U M E R Y

wood oil ; (2) an miknonTi wood of weak odour ; and (3) Bois de
Giiron de Cayenne, also sold as cayenne sassafras wood. TMs is
the wood which yields cayenne linaloe oil. It is the product of a
tree for which the native Indian name is Licari Kanali, and is
known the French inhabitants as Bois de Rose male. The
wood known to the French inliabitants as Bois de Rose femelle
appears to be the product of Protium altissimum [Idea altissima).
This has a lemon-bergamot odour, and differs entirely from Bois
de Rose male.

So that what is known in Europe as oil of Bois de Rose femelle
is, in fact, derived from Bois de Rose male, the oil from the Bois
de Rose femelle not being a commercial article at all. Aublet
named the tree Licari guianensis (“ Plantes de Guiane Frangaise,”
p. 313), but, after fuller investigations. Dr. Moeller showed that
there vms little doubt that the tree was Ocotea candata. It may
be therefore taken for granted that oil of Bois de Rose femelle,
or ca 3 'enne linaloe oil, is the product of the wood of Ocotea caiidaia,
known in Guiana as Bois de Rose male. The oil obtained by the
distillation of the wood is a colourless or pale j'^eUow oil of soft,
sweet odour, in which that of its principal constituent, hnalol,
predominates. It is used for the manufacture of linalyl acetate,
the basis of artificial bergamot oil, and as a constituent of such
perfumes as lily of the valley, hawthorn, honeysuckle, jonquil, and
corylopsis.

The pm’e essential oil usually has the following characters :
specific gravity, from 0-870 to 0-882 ; optical rotation from — 9°
to — 18° ; and refractive index, 1-4600 to 1-4640. It contains
only a very small quantity of esters, but from 60 to 80 per cent.,
sometimes even 90 per cent., of free hnalol. It is soluble in
2 volumes of 70 per cent, alcohol. In determining the total
alcohols in the oil, as in aU oils containing much linalol, special
precautions must be taken, or the linalol will be decomposed in
the process. To acetylate the oil it should be dissolved in four
times its volume of xjdene and boiled for about five hours.
[Vide “ Alcohols, Determination of.”)

Messrs. Chins & Co_. [Les Parfums de France, 1924, 13, 50)
have found that many genuine, samples of this oil distilled by
themselves have specific gravities up to 0-886. They consider
that acetylation in xylene solution gives too low results, and
that formylation for eighty-four hours in the cold (about 25°)
and saponification for ninety minutes give the, most accurate
determination of the hnalol present.

PEBFU Mini Y

A terpeneless oil of Bois tie Bose is sometimes offered as being
higlil.y concentrated. When it is remembered that the natural
oil contains 60 to 90 per cent, of the active constituent, it is
obvious that there is not much room for concentration, so tliat
in this case the terpeneless oil possesses but little advantage over
the natural oil.

In addition to linalol, the oil contams gcraniol, terpineol, cineol,
dipcntenc, traces of furfurol, mcth 3 *l-heptenone, nerol, and
probablj' isovaleric aldch 3 "de. Bonre-Berlrand Fils {Bulletin,
October, 1909, 40) give the following as the composition of the
oil : —

j\Ieth 3 'l-licptcnone
i/ccro-linalol .
D&rh'o-terpineol
Gcraniol .

Nerol

Other bodies .

Tracc.s.
90-5 per cent.

0 - .3
2-4

1 - 2
0-6

BOKHARA GLOVER.— This plant, 3Ielilotiis alba, is a
favourite vdth bees on account of the nectar present in the white
clover blossoms. It is one of the conti'ibutoiy causes of the
perfume of new-movm ha 3 ’', a perfume which is to some extent
imitated b 3 r using coumarin as the basic material.

BORNEO CAMPHOR. — ^This name is the common name for
tZc.'Clro-borneol. It is also termed Baros camphor, Mala 3 ’' camphor,
and Sumatra camphor. (Vide ” Borneol.”)

BORNEO CAMPHOR OIL.— The wood of Dnjobalanojis
aromalica, the so-caUed Borneo camphor tree, 3 delds this odorous
essential oil, which contains de.rZro-borneol. It is not often seen
in commerce, and is a colomless or pale 3 'ellow oil of specific
gravity 0'918 ; optical rotation, + 11° ; and refractive index,
1-4885. It contains pinene, camphene, d-borneol, dipentene,
terpineol, and sesquiterpenes.

BORNEOL. — ^Borneol CioHj^OH is the alcohol corresponding
to the ketone camphor. It occurs naturall 3 ^ as de.rZro-borneol in
Dryobalanops campUora, and as Zcct’o-borneol in Blumsa balsamifera.
It forms crystalline masses or fine needle-like crystals, which melt
at 204° and boil at 212°. Numerous oils of pine needles, derived
from Abies and Pvnis species, contain both free borneol and
bornyl esters. It is also produced artificially by reducing camphor
with sodium. Borneol forms a well-defined series of esters with
organic acids of which bornyl acetate is the principal, and rvhich

99 ' 7—2

PBJRFU ME 1{ Y

lias a fine pine needle odour. Tlie following method may he used
for distinguishing between borneol and isoborneol. The alcohol
to be tested is dissolved in about ten times its weight of pyridine,
and the calculated quantity of ^a?'o-nitrobonzoyl chloride added,
and the mixture heated on a vaater bath for several hours. The
J)'^Tidine is removed 113 ^^ extracting with ice-cold dilute sulphuric
acid, and the paw-nitrobenzoate of the alcohol is separated, dried,
and 'recrystallised from alcohol. The borneol compound melts
at 137°, whilst the isoborneol compound melts at 129°.

BORNYL ACETATE. — ^Borneol itself occurs in the free
state to a large extent in certain pine needle oils, spike lavender
oil, etc. Its acetic ester, born 3 d acetate, C 10 H 17 .O 0 C.CH 3 , is found
in certain pine needle and other oils, and is a substance of ver 3 ’'
refreshing odour, recalhng that of a pine forest. It is manufactured
artificial!}’' by the esterification of borneol by acetic anh 3 ’'di‘ide,
and, when pure, is a ciystalline solid melting at 29°, of specific
gravity about 0-990. Its refractive index is 1-4645 at 15°, and
boiling point 9 S° at 10 mm. pressure. When liquefied, it often
remains liquid without solidif 3 dng for a considerable period. The
commercial article is a mixture of born 3 d and isoborn}’’! acetates,
having an optical rotation about -f- 20 °.

BORNYL BUTYRATE. — This ester, of the formula
C 10 H 17 O 0 C.C 3 H 7 , is very similar to the acetic ester, but is rather
more camphoraceous in odour. It is a liquid boiling at 121 ° at
10 mm., and having a specific gravit}’' 0-996 ; optical rotation,
-|- 22° ; and refractive index, 1-4638 at 15°.

BORNYL FORMATE.— This ester, O 10 H 17 OOCH, is manu-
factured artificially, and is a liquid of specific gravity 1-013 ;
refractive index, 1-4708 ; and boiling point, 90° at 10 mm.
pressm’e. It has a refreshing pine odom’, and is useful for blending
with borneol and all its esters. The commercial article is a
mixture of bornyl and isoborn 5 d formates, having an optical
rotation about — 47°.

BORNYL PROPIONATE.— Although obtainable commer-
cially, this ester, C 10 H 17 .O 2 C.C 2 H 5 , is not often used in perfumery,
as it does not differ very materially in odour from the butyrate.
It is a liquid of specific gravity 0-978 ; optical rotation, -j- 24° ;
and refractive index, 1-4643. It boils at 110 ° at 10 mm.

BORNYL VALERIANATE.— No higher ester of borneol is
manufactured than this body, which actually is principally the

100

PERFUMERl

isovalerianate of the formula CioHi^OgC.C^Hg. It is a liquid
having a specific gravity about 0-956 ; optical rotation, -{- 15°
to + 20° ; refractive index, 1-4628 ; and boiling point, 130° at
10 mm. It has a rather more fruity odour than the lower esters
of borneol.

BORONIA, OILS OF . — Boronia ihujona is a tall shrub
growing in Xew South Wales. The leaves and terminal branchlets
yield about 0-5 per cent, of an essential oil which is coloiu-less,
with a slight fluorescence, and an exquisite odour of black currants.
It has a specific gra\dty 0-912 to 0-915 ; optical rotation, + 13°
to ■— 56° ; and refi-active index, 1-4524 to 1-4569. It contains
80 to 90 per cent, of thujone, thiijol, esters, a sesquiterpene, and
a paraffin hydrocarbon. H. G. Smith {Proc. Roy. Soc. Victoria,
1919, 32, i.) has examined the oil from Boronia 'pinnaia, which
has a rose-geranium odour. It has the following characters ; —

Specific gravity at 15° .

Optical rotation .....
Refractive index at 20° ....

Saponification number (on heating) .
Saponification number (in the cold) .
Geranyl acetate .....
Saponification number on heating, after
acetylation . . . . .

Saponification number after acetylation in
the cold ......

1-0197
+ 3° 8'
1-5125
20-2
18-3

6-4 per cent.
36-9
27-7

According to the author, the oil of Boronia pinnata contains
free and combined geraniol as acetate and butyrate, trimethyl-
gallic acid, and 70 per cent, of elemicine.

BOSWELLIA RESIN. — ^Tliis important gum resin, known-as
olibanum or franlcincense, is of considerable value to the perfumer,
and is used, as its common name would imply, in the manufacture
of incense. The name olibanum is to some extent of common
origin with that of gum benjamin {q.v.). It is derived from the
Hebrew word Ichonali, meaning milk, through the Arab Luhan,
meaning incense, and was known to the Greeks as Libanos, and
to the Romans as Olibanum. E. M. Holmes (P. & E. 0. R., 1916,
79), in a paper dealing exhaustively vdth this substance, quotes
the following method of trading between the natives who collect
gold and the traders, who do not understand each other’s .
languages. ” The gold caravan, which consists of some 500 traders,
arrives in the highlands of Abyssinia, and brings with it salt

101

BVCL

12314

668.54

P247P

PERFUMERY

and iron and cattle, and set up a hedge against which they place
joints of meat, salt and iron, and then retire. - The natives then
ap])roach, and each places what gold he considers adequate on
what ho fancies. They, too, then retire. The traders then return
and inspect wdiat has been offered. If content, they remove the
gold and leave the goods in exchange ; otherwise, they again
retire and leave the natives to again approach. This they do, and
either place more gold on the goods or take wdiat they’ had
previously left, if they do not consider the goods of an}'- higher
value.” The collection of frankincense in the early days appears
to have been carried out on a similar basis. Aecording to Holmes
(Zoc. ni.), the libanotophoros or frankincense -}delding region of
the old Sahseans in Arabia wns visited by Carter in 1844-1846, and
is stated by him to extend on the southern coast from 52° 47' to
58° 28' E. longitude, and a frankincense tree found there w'as
described and illustrated by him in the Journal of the Bombay
Branch of the Royal Asiatic Society, vol. 11, tab. 23, and subse-
quently named after him as Bosivellia Carleri by Dr. (now Sir G )
Birdwood.

Whether the ancient Sabaians derived any portion of frank-
uicense from the opposite coast of Africa, now known as Somali-
land, is uncertain, although they w’ere in the time of Solomon
(1000 B.c.) in constant communication with the natives of that
region, but that it did produce olibanum wns midoubtedly known
to the Homans in the time of Strabo and Ai’rian of Alexandra,
since the latter (a.d. 54r-68) states in the “ Periplus of the
Erytlu’fean Sea ” that olibanum wns exported thence, partly to
Eg}q3t and partly to Barbaricon, at the mouth of the Indus. At
that period the whole of the coast of modern Somaliland from
Zeyla (then called Aulites) to Cape Gardafui (then called Promon-
tarius Aromaium) wvas known as Barbarica, and the eastern
portion of it as Regio Cinnamomifera, w'here cinnamon Wns
supposed to be produced, since the Romans imported it from the
port of Mosyllum on that coast. This should not be surprising,
since in modern times m}nrh wns ealled “ Turkey myrrh,” and
rhubarb “Turkey and East Indian rhubarb,” long after their
geographical scurce was known, and, similarly, Goa pow'der is
now known not to be produced at Goa in India, but in Brazil.
It seems probable, though it is not certain, that during the Roman
occupation of Egypt the trade in frankmcense, which w'as
previously centred in Moscha, near Bhofar, the ancient emporium
on the south Arabian coast, may have been diverted to Mosyllum,

102

PERF U HER y

a port on the opposite African coast, which was in the very centre
of the African frankincense-bearing region.

Tile authors of “ Pharmacographia ” (1879) state that, at that
date, the ohbanum of Arabia was shipped, from several small
places on the Arabian coast between Damkote and A1 Kammar,
but the quantity produced in this district is much below that
furnished by the Somali country in Eastern Africa.” The Somali
franlcincense is sliipped from Bunder Murrayah, Berbera, and
many smaller ports to Aden, or direct to Bombay. The trade is
eliiefly in the hands of the Banians, and the great emporium of
the ^ug is Bombay, but a certain portion is shipped through the
Straits of Bab-el-Mandeb to Jiddah, according to Von Kremer,
to the value of £12,000 annually.

It does not seem clear from the context whether the native
Arabs still collect franlcincense in southern Arabia, since the
authors quote the statement of Captain Mes (Joicr. Roy. Geog.
Soc., 1872, vol. xxii., p. 65} that the drug is not collected by the
people of the country, but by Somalis, who cross over in numbers
to the Arabian coast, pa 3 dng the Arab tribes for the privilege, and,
further, that it would even appear that the names of Luhan Maher i,
or Mascati, or Sheehaz, referring to places on the coast of Arabia
between 52° 10' and 54° 32' E. longitude, are now apphed to
olibanum brought from the opposite African coast. The authors
also state that “ Hddebrandt informed one of us (December, 1878)
that he has ascertained at Aden that all the franlcincense imported
into Aden comes from Africa.”

The latter statement does not quite agree with that of Vaughan,
who in 1853, in a paper on “ The Drugs observed at Aden ’’
(communicated by D. Hanbmy to the Pharm. Jour. (1), xii.,
p. 229), states that a large quantity of olibanum is collected in
the southern and south-eastern districts -of Ai-abia and exported
from several towns on the coast between Has Eartak and Marbat,
the famous thuriferous region which proved the object of such
diligent search in ancient times.

Vaughan also describes several commercial sorts of African
frankincense occurring in the Aden bazaar, and there known by
the names of Luhan Mattee, Zniban Malcur, and Luhan Berber a
or Mustika, named after the ports from which they are exported
to Aden. The most important of- these are : (1) lAihan Berhera,
which is coUected by the Ayil Yunis and Ayil Hamed tribes in
the west of Somaliland and brought in to Berbera ; (2) Luhan
Hunkur or Aungure, coUected by the Dour Mohammed and

103

PE RF U MEBY

Abarclagaliala tribes in central Somaliland and brought to the
port of Aungure ; (3) the Lvban Maknr, which is collected in the
east of Somaliland by the Worsungali and Meggertein Somalis in
May, June and Julj^ and carried to the neighbouring ports, such
as Bunder Koor and Bunder Kassooin, and is nearly all taken
across to Maculla and Shehr, on the Arabian coast. This possibly
comes back to Aden as the Lvhan tShoharrec or Liihan Morhat,
supposed by Vaughan to be produced in Ai’abia.

The L'liban Ilaflce described by Vaughan is collected chiefly
b}^ the Abardagahala tribe in central Somaliland and brought to
the port of Llaiti, near to the ancient Mos3dlum, for export, whence
the name of Liihan Maili or Maycti.

Vaughan also distinetty affirms that three baggalas were annual^
freighted from ]\Iarbat to Bombaj’' with an enthc cargo of the
Arabian frankincense, which realises a higher price in the market
than an}’ of the qualities exported from Africa. The onlj^ jDrobable
explanation of these contradictory statements is that frankincense
is collected in Arabia b}’ Somalis and exported dhect to Bomba}'',
and that some of it is sent back from Bombay to Aden cn route
for Eurojoe.

The latest account of the frankincense region of Somaliland is
given by Dr. E. Drakc-Brockman, E.B-.G.S., in “ British Soinah-
land ” (1914). He states that the drug is produced in the coast
regions, more especially those occupied by the Habr Toljaala,
Warsangah, and Mijcrtain tribes, and that the di’ug is known to
the Somalis as Beyo or Hanjibeyo ; also that there arc two distinct
varieties, ealled by the Arabians Loban Dakar and Loban Ilaidi,
i.e., male and female frairkincense respectively. The tree yielding
Loban Dakar is called by the Somalis IloJior or Molmr, and is
Boswellia Carferi, wliilst the tree yielding Loban MakJa is called
Ycliar, and is BosicelUa-Frcreana,

The former is found on the maritime limestone mountainb
eight miles south of Berbera in western Somaliland, and thence
eastwards, whilst BosiccUia Frereana is not found until the Habr
Toljaala country is reached, and extends further west into the
country of the Warsangali and Mrjertain tribes.

B. Carieri was first described by Speke as a tree with rugged
bark and smooth epidermis of a reddish tinge, pleasant aromatic
odour, and strong astringent flavom’, and as used for tanning
skins. Powdered and sprinkled dry on a wound, it acted as a
styptic. Dr. Drake-Brockman describes- the freshly collected
drug as follows : Both the varieties are found in small tears, and

104

PERFUMERY

are mixed up with bark, sand, and other foreign matters, and
have to be sorted, which is usually done at Aden, the picked
samples of Loban Dakar being sent to Europe, whilst the Eoba^
Maidi is sent to India and Egypt. The inferior qualities of each
are done up separately in sacks of matting and sliipped back to
Africa most of it finding its way to Abyssinia. The Loban Dakar
is shipped from Aden to London and Hamburg, where it is made
into false amber beads, which are threaded into necklaces and
rosaries, much w^om by the Arab and Somali wmruen. The tears
of the two kinds are not difficult to distinguish, the tears of Loban
Dakar beiug usually darker and of a more amber colour ; the tears
of Loban Maidi are paler and clear like a topaz. The latter, when
packed, generally becomes formed into large masses, whilst the
Loban Dakar, being drier and more friable, does not usually con-
glomerate so readily, and does not form so plastic a mass when
chewed. In the form of emulsion, it is sometimes given for venereal
complaints. The Loban Maidi is chewed by the Somalis, and is
sometimes used in the chewed state as a cement. A variety of
Loban Maidi is sometimes found in large stalactitic pieces formed
by the oozing and trickling down of the milky juice. These pieces
may be 6 inches or more long and 3 or 4 broad, and present a
characteristic appearance, having an irregular surface with many
small protuberances and being covered with white powdery
streaks, and, when fractured, showing alternate white and clear
layers, and on the under surface often have pieces of the papery
outer bark attached.

The colour varies in both kinds, being often pale in the Loban
Dakar and deep orange in the Loban Maidi. The Loban Dakar
is sometimes found in pieces the size of a hen’s egg, but is then
invariably composed of small agglomerated tears.

As regards the name Beyo and Hanji-beyo, Dr. Drake-Brockman
explains that the prefix Hanji is applied to any gum resin that is
used for chewing. It therefore applies more strictly to the
Loban Maidi, which is used for that purpose.

In- Bombay frankincense passes through the Custom House
under the name of Es^ {Isas of Drake-Brockman), and is there
sorted into four or five different qualities, the first, consisting of
large clear tears, being destined for the European market. The
intermediate qualities, as well as the last, knoAvn by the Indian
name of Dhup, consisting of pieces of the bark coated with
frankincense, supply the Indian or Chinese market.

The Mahometan writers describe five kinds under the Sanscrit

lO.'i

P E R F U 3{ ERY

name of Knndnr, as follows : (1) Kundur Zahar, or male frank-
ineense, in deep yellow tears ; (2) Kundur Unsa, or female

frankincense ; (3) Kundur lladahroj, artificial tears made by

shaking the moist exudation in a basket ; (4) K^indur Kisliar, or
Kaslifar, consisting of pieces of bark covered with the exudation,
identical with the Dhuj:) already mentioned ; (5) Kxmdur Duhak,
or dust of olibanum. In the London market there are three
principal forms recognised : ordinary, consisting of irregular or
more or less oval or pyriform tears, and garblings and siftings. The
fine large tears known at Aden as Liiban Fasons Bedoiv come from
the ]\Iijertain district, in the east of Somaliland. The Liiban 3'Iaidi
of Drake-Brockman comes from the same district, but is not a
regular article of importation into this countr3^ A very fine
specimen of it exists in the museum of the Pharmaceutical Society
at Bloomsbiuy Square, presented some 3"ears ago b3’- Mons. Cesar
Chantre, a French silk merchant, then residing in London, a
native of L3mns, who made a hobb3' of the stud3^ of the London
drug market, and acquii’ed a fine collection, which he subsequenth^
presented to Dr. Cauvet, a professor of materia medica in his
native cit3% who published a few 3’-ears afterwards a little known,
but most concise, reliable, and almost enc3J'clops3dic work on
materia medica.

Until the middle of the last centuiy but little v^as known to
botanists concerning the trees that 3deld the ohbanum of com-
merce. In 1846 Dr. J. Forbes Royle suggested, in an article in the
Pharmaceutical Journal, vol. v., j). 543, that African olibanum was
probably the produce of a species of Bosivellia of the natural order
Burseracecc. It was only in 1870 that Dr. (now Sir G.) Buxlwood
was able to describe as sources of olibanum, Bosivellia Gartcri,
obtained b5’' H. J. Carter in 1848 on the south-east coast of Ai’abia ;
Bosivellia Bhau-Dajiana, obtained b3’- Colonel Pla3dair ; and
Bosivellia, Frereana, from eastern Somaliland, the last-named being
the soiu’ce of the rarer fiankincense knovm b3^ the Arab name of
Luhan Ilaidi, Ilaitee, or Ilaiyeti. The species are not the onty
ones that 3deld frankmcense, since there are several others men-
tioned in “ Pharmacographia ” from which it is collected, but it
is doubtful whether the3^ are species or only forms growmg under
different conditions, some of them occurring on limestone hills
and valleys in the neighbourhood of the sea, sometimes in lime-
stone detritus, and others growing out of the rocks on the high
and precipitous mountain ranges further inland.

One of those referred to, B. Garteri, is called b3'- the natives 3Iohr

106

PERFUMERY

Meddii- or Madow, i.e., black molir tree, and another referred to,
B. Frcreana, is called Mahor in Sennaar. Dr. Malcolmson describes
one of these as growing at about 1 ,000 feet on the hills near Bunder
Marraj'ah (11° 43' N. latitude) to a height or40 feet, firmly attached
to the bare limestone by a mass of vegetable substance, part of
the tree, ■which sends roots into the cre'vices of the rock to an
immense depth.

-The trees have jmmate leaves recalling in appearance those of
the mountain ash, but hany, the branches having panicles of small
fragrant greenish flowers. The whole plant contains the fragrant
gum resin, which exudes even from the flowers, when injured, as
a miUiy juice. The collection of the frankincense is described by
Cruttenden, who -visited the Somali country near Bunder Mun-
ra}^!! in 1843, as follows : “ About the end of February or the
beginning of March, dming the hot season, the Bedouins visit all
the trees in succession and make a deep incision in each, peeling
off a narrow strip of bark for about 5 inches below the wound.
This is left for a month, when a fresh incision is made in the same
place, but deeper. A third month elapses, and the operation is
again repeated, after which the gum is supposed to have attained
a proper degree of consistency. The mountain sides are immedi-
ately covered with parties of meji and boys, wdio scrape off the
large clear globules into a basket, wlulst the inferior quality that
has run dowm the tree is packed separately. The gum, when first
taken from the tree, is soft, but hardens rapidl3^ Every fortnight
the mountains are visited in this manner, the trees producing
larger quantities as the season advances, until the middle of
September, when the first shower of rain puts a close to the
gathermg for that year.”

The collection of the di’ug in southern Arabia is described by
Carter as follows ; “ The gum is procm-ed by making longitudinal
incisions through the bark in the months of May and December,
when the cuticle glistens with intumescence from the distended
state of the part beneath. On its first appearance the gum comes
forth white as millc, and, according to the degree of fluidity, finds
its w^ay to the ground, or concretes on the 'branch near the place
from which it first issued, whence it is collected by the men
and boys employed to look after the.trees by the different families
wFo possess the land in which they gi’ow.”

Hildebrandt, speaking of the collection of Luhan Meithi, Maiti,
or Maidi, near Lasgori, in Somaliland, from the Gekar (Yegaar)
trees, states that the thick, low trunlt of the tree grows out of the

107

PEBFU MERJ

nearly perpendicular rock, and that the flowers were just blossom-
ing on March 25th. The Somali men and women reach the trees
by very dangerous ijaths, and make incisions, and after only six
days collect the resin. The L^iban Haiti does not contain gum,
but only oil and resin, and therefore probably dries more quickty
than the ordinary frankincense. He remarks that it is sold at
Aden and Geddah (Djedda), and thence finds its way as a masti-
catory to the harems, and is also chewed bj'’ the Somalis when
they are tired.

It is noteworthj'- that it does not seem to have been utilised for
this purpose, for which its pleasant odour and possibly antiseptic
properties should render it useful.

Pure olibanum has, according to Kremcl, the following
characters : —

Percentage of resin

72-1

Acid value of resin

59-3

46-8

50-3

Ester value of resin

G-6

41-0

60-5

iSaponification value of resin .

G5-9

87-8 '

110-8

Sample No. 1, however, is probabty quite abnormal.

Olibanum contains a small amount of essential oil, var 3 ’ing from
5 to 10 per cent., which is a pale j’^ellow liquid of balsamic odour,
having a specific gravity 0-87o to 0-894 ; optical rotation, -j- 15°
to + 30° ; and refractive index, 1-4725 to 1-4825. It contains
a-pinene, camphene, dipentene, para-cymane, and an alcohol of
the formula CioHjgO which has been named olibanol. Borneol
esters are present in traces.

Boswellia sonata is a native of north-west India, and jdelds a
somewhat similar resin. Apparentlj^ there are two well-recognised
varieties, the foliola ovato-oblonga and the foliola lineari-lanceo-
lata. The resin is collected in the Punjab twice a j^’ear. It is
used for medicinal pm'poses, and is also burned as incense in
rehgious ceremonials. Experiments have been carried out recentty
at the Forest Research Institute at Delna Dun vith a view to
determining the most advantageous method of treating the crude
gum resin in order to separate the essential oil, the purified resin,
and the gum. The crude gum resin is placed in a still vdth a
perforated false bottom, and steam is passed through the mass.
Most of the resin and oil passes through, and collects at the bottom

108

PEBFU MERY

of the still, whilst the gum and impurities remain on the false
bottom. The oil is then separated from the resin by steam
distillation, and the oil so obtained is rectified, and then consists
of almost pure pinene. From experiments on this oil carried out
at the Imperial Institute it was found that this oil dissolves
varnish resins, such as dammar, sandarac and soft copal, and
varnishes prepai’cd vdth it dried with a less lustrous surface, but
more rapidly, than those made with ordinary turpentine.

Tinctures of olibanum are used as fixatives, and also in the
preparation of heavy Oriental odours. Peiiumes containing
champaca and perfumes of the broom type are improved by
traces of olibanum, Olibanum is sometimes IcnoA^m as gum Thus.
(See also under “ Incense.”)

BOUVARDIA.— This is a fancy name, of considerable popu-
larity, for a perfume somewhat resembling jasmin in type. It
is based on such synthetic perfumes as benzyl acetate, hydroxy-
citronellal and phenjd-ethyl acetate.

BRILLIANTINES.— These are merely mixtures of perfume
and oil used as di’essings for the hair. They are usually mixtures
of an alcoholic solution of perfume with olive, almond, castor or
petroleum oils, wliich require shaking before \ise, or are simply
these or similar oils to which a trace of absolute perfumes, free
from alcohol, has been added, thus forming a one-solution
brilliantine.

BRISBANE WHITE SASSAFRAS, OIL OF.— The tree
known in Queensland as the Avhite sassafras is a species of
cinnamon, Cinnamomiim oJiveri. The bark yields an essential
oil of specific gravity 1-030, and refractive index 1-5165 at 23°.
It contains about 12 to 15 per cent, of pinene, IS to 20 per cent,
of camj)hor, 25 to 27 per cent, of safrol, and 40 to 45 per cent, of
eugenol meth3d ether {Jour. Cheni. Soc., 1916, 751).

BROMACETAL.— Bromacetal is an important intermediate
product in the mariufactui’c of phenyl-acetic aldehyde, the well-
known artificial hyacinth base. It has the formula CHjBr.CH
(0.C2H5)2, and boils at 82° at a pressure of 28 mm. It results
by adding, very gradually, 51 c.c. of bromine to 45 grams of
paraldehyde kept at a temperature of some degrees below freezing
point. After the crystalline mass has liquefied, 200 c.c. of absolute
alcohol are added and the mixture allowed to stand for twelve
hours. Bromacetal is not itself used as such in perfumery.

109

PERFUMERY

BROMELIA. — p - iiaplitliol - nietltyl - ether and p - naphthol-
eth 5 d ether are Wo well-known artificial perfume materials which
are kno\vn as nerolin. The former is also known as yara-yara,
whilst the ethyl ether is knoum as bromelia. These bodies have
the formula C 10 H 7 O.R, where R is the methyl or ethyl radicle. -

Both have a pronounced neroli odour, that of the ethyl ether
being rather the finer, with a suggestion of pmeapple. Yara-yara
melts at 72°, and bromelia at 37°. They may be prepared by
heating -/?-naphthol-sodium vith methyl, (ethyl) iodide in methyl
(ethyl) alcohol. One thousand parts 'of 90 per cent, alcohol
dissolves about 20 grams of yara-yara, and 40 grams of bromelia.

BROMOSTYROLENE. — This body, of the formula
CgHj.CH : CHBr, is a very important synthetic perfume. It is
used to a very considerable extent (as is also phenyl-acetic
aldehyde {q.v.) ) as the basis of perfumes of the type of hyacinth,
narcissus and jonquil. It is employed very extensively in soap
perfumery. St 3 T:olene, CgHg, yields two series of halogen deriva-
tives, the cu -derivatives and the a-derivatives. For example,
co-bromostju'olene is CgHg.CH : CHBr, and a-styrolene is Cgllj.
CBr : CHo. The a-derivatives are useless for perfumery purposes,
while the w-compounds are highly odorous. w-Bromostyrolene
is prepared b}^ treatmg cinnamic acid vdth bromine to saturate
the double linlcage, and 'a molecule of hj^’drobromic acid is
abstracted by means of caustic aUcali. Levdnsohn (P. c& E. 0. R.,
1924, 119) gives the folloving method for its manufactiue.
Bromostjuolene is formed from cinnamic acid according to the
following equations : —

(1) CgHg.CH : CH.COOH -f Br^ = CcH5.CHBr.CHBr.COOH

Cinnamic acid Dibromocinnamic acid

(2) CcHg.CHBr.CHBr.COOH -b Na.COg =

Dibromocinnamic acid

CcHg.CH : CHBr -{- NaBr + COg -f HaHCOg.

Bromost^Tolene

Ten kilograms of cmnamic acid and 40 kg. of ether are placed
in a mixing vessel, wliich is provided with an exceptionally good
condenser, having a large cooling surface. A means of injecting
live steam is also provided.

Eleven kilograms of bromine (3,670 c.c.) are then slowly
introduced by means of a dropping funnel during continuous
stirring and strong cooling of the reflux condenser. When the
addition of the bromine is complete, the stirring is continued for
some hours, and the ether distflled off — ^the condenser being

110

FERFU MEJll

connected to the still by means of a three-way cock, so as to allow
this operation 'to be condncted by merely tnming the cock. As
-soon as the ether has been completely removed, a solution of
7 kg. of soda ash in 20 kg. of water is added, and the reaction
mixture steam distUled. The bromostyrol distils over with the
water and collects on the bottom of the receiver. It is rectified
under diminished pressure. Boiling point, 98° to 99° at 5 mm.
Bromostyrol turns brown in daylight, and must be kept in the
dark.

a-BromostjTolene, CgHgCBr ; CHo, is a very unstable substance,
of no value in perfumery. The commercial article, co-bromo-
styrolene, CgHg.CH : CHBr, can, theoretically, exist in two
stereoisomeric forms.

Dufraisse {Comptes Bendus, 1920, 171, 960) has prepared the
second isomer by the action of caustic soda on bromobenzal-
acetophenone. According to Dufraisse the two stereoisomers have
tile following characters : —

Commercial

oj-bromostyrolene.

Specific gravity at 20° . 1-4220

Refractive index . ' . 1-6094

Boihng point at 22 mm. •. 107°

Boihng point at 760 mm. 220°
Melting point . . -f 7°

Stereoisomeric

variety.

1-4260

1-5990

71° (at 6 mm.)
- 8 °

A. G.

BROOM. — ^The flowers of Sarofliamnm scoparius, and pos-
sibly allied plants, are cultivated in Provence, and the perfume
extracted, in the form of concrete or absolute, by means of volatile
solvents. The perfume, known as “ genet,” is also known as an
artiflcial preparation, which usually contains some natural
-perfume and various synthetics, including para-cresol methyl
ether.

BRUYERB D’ANNAM. — Baechea frutescens is a plant
formd in southern China and in Cochin China, where it is known
as Bruyere d’Annam. It yields an essential oil having a specific
gravity 0-890 ; optical rotation, — 4° 34' ; refractive index,
1-4754 ; acid value, 1-9 ; ester value, 3-7 ; and ester value after
acetylation, 44-8. It probably contains Hnalol and cymene.
Eucalyptol is also present. This oil has also been described as
“ essence de Bruyere de Tonkin.” The plant is in full flower in
August. .Distillafion commences in January, and the oil varies
to a slight extent with the locality in which it is distilled. It is
used in France for the perfuming of 5oap.

Ill

PERFUMERY

There appear to be two oils distilled from the plant under
different conditions, one oil being j^ellow and the other green in
colour. They have both been examined by Gattefosse, and also
by Roure-Beiirand Fils {La Parfimcrie MocUrnc, 1923, 108, and
Bulletin, Rourc-Beriraiul Fils, April, 1914, 6). The oils had the
following characters : —

Yelloii) Oil

Specific gravit}^ at 15°
Optical rotafiori .
Refractive index .
Esters

Free alcohols
Aldehydes .

Specific gravity at 15
Optical rotation .
Refractive index .
E';tcrs

Free alcohols

Galtofossc.

Bertrand.

. 0-8885

0-88G2

. - 6° 5' . .

— 1° 22'

, 1-4790

—

2-lG per cent.

3-5 per cent.

. 12-97 „

—

. 5-2 „

3-5 „

Green Oil

° . 0-8895

0-8871

. - 0° G'

— 4° 40'

. 1-4772

—

3-G per cent.

1-2 per cent.

. 11-3

—

Up to 1923 tliis oil was regarded as the product of Cailicius
fasciculata, which is now known to be erroneous.

BUCHU OIL. — ^This oil is not used to any extent in perfumery,
but in the preparation of flavours having a black currant odour
or taste a small amount of it is sometimes emi)lo 3 ^ed. There are
several species of buchu used for the distillation of the oil, of
which the principal are Barosma scrratifolio, B. heiulina and
B. crenulata. The leaves ^neld from 1 to 2 per cent, of oil. It
contains limonenc, dipentene, a ketone which is probably Imvo-
raenthono, and a crystalline body known as diosphenol, CioHjcOa,
melting at 83°. This body occurs principally in the oil from
B. heiulina. There is a species of barosma, B. j^Mcliella, wliich
jnelds an oil having the odour of citronella. The four oils referred
to have the following characters : —

Specific gravity.

Eolation.

Eofraotivo index.

B. heiulina

0-935 — 0-970

r-H

1-4740— 1-4865

B. crenulata

0-935

— 15°

.1-4800

B. serratifolia .

0-918 — 0-960

— 12° to — 3G°

—

B. ptilchella

0-885

+ 8° 30'

1-4575

112

PERFU MTSB Y

BULNESIA SARMIENTI.— This tree yields the wood
known as Palo santo (holy wood) or Palo hahama to the inhabitants
of Argentina and Paraguay. The tree grows very freely along
the course of the Rio Bermejo, a tributary of the Bio Paraguay.
The wood yields from 4 to 8 per cent, of a semi-solid essential oil,
w'hich is known as guaiao wnod oil or guaiacum wood oil, as it
was at one time ei*roneously believed to be derived from Guaiacum
officinale. It has also been knovn in commerce as champaca
wood oil. It has a very fine and delicate odom’, and is weU adapted
for blending vdth more powerful perfumes. Apart from its
legitimate use, it is sometimes used as an adulterant of otto of
roses. It melts at from 42° to 50°, and has a specific gravity
0-9G5 to 0'975 at 30° ; optical rotation, — 3° to — 8° ; and
refractive index, 1*5030 to 1*5050 at melting point. The only
well-ascertained constituent present is' the alcohol guaiol, CigHooO.

BUPLEUROL. — ^This body is an alcohol of the formula
C 10 H 20 O* ^ found in the essential oil of Btipleurum Jrulicosu,m.

It has a faint rose odour) and has a specific gravity 0*849 ; optical
rotation, 0° ; refractive index, 1*4508 ; and boiling point, 209° to
210 °.

BUPLEURUM FRUITICOSUM.— This umbelliferous plant
grows wild in Sardinia. The flowers and leaves contain an essential
oil of specific gravity 0*830 to 0-8G9 ; optical rotation -f- 19° to

47° ; and refractive index, 1*4783 to 1*48G2. It contains an
alcohol, winch has been named bupleurol (g.v.), which has a slight
but distinct odour of roses. (See^«. R.Accad. Lined, -1913, 22, 34.)

BURSERA OILS.— See “Linaloe Oil.”

BUTNERIA OCGIDENTALIS, OIL OF.— The leaves and
twigs of this plant, also known as CalycaniJms Occidentalis, yield
a small quantity of a fragrant essential oil of specific gravity
0*930 ; optical rotation, + 7° ; and refractive index, 1*4710. It
contains eucalyptol, pinene, borneol, linaljd acetate, camphor,
methyl salicylate, and a sesquiterpene alcohol.

BUTYL ESTERS. (See also “Butyl Phenyl Acetate.”) —
The esters of butyl alcohol are of a fruity or floral odour, the
principal of them having the characters shown in the table on p.
114, as met with in commerce (Durrans, P. ds E. 0. B., 1924, 226).

BUTYL PHENYL ACETATE.— This ester, of the formula
C 4 HgC 02 .CH 2 .CeIl 6 , is a colourless oil having an odour recalling
that of carnation. It is only used in small quantities, and gives
s* 113

PBBFV MERY

Specific gravity.

Eefractivo index:.

Boiling point.

Butjd acetate .

0 - 880 - 0-882

i 23 °- 127 °

,, benzoate

1 - 0085 - 1-0090

1 - 4975 - 1-4980

247 °

„ bul3U’ate

0-871

1-4050

160 °- 165 °

„ formate .

0-9108

—

106 °- 107 °

,, phenjd acetate .

0-9969

1-4890

260 °

„ propionate

0-8828

—

145 °- 146 °

„ salicylate

1-076

1-5110

266 °- 207 °

„ valerianate

0-8648

1-4109

170 °- 175 °

character to the various types of carnation bouquets. Its isomer,
isobutyl phenyl acetate, is of a much finer odour, and is known
as “ eglantine ” or “ ideal base.” It is used as the basis of most
perfumes offered under the name “ eglantine,” and is also useful
in carnation and rose odours. It has a specific gravity 1-104, and
refractive index 1-5570.

BUTYRIC ALDEHYDE, — ^Butyric aldehj^de, C 3 H;.'COH, is
an aldehyde with a pronounced sharp odour, occurrnig in oils of '
eucalyptus and cajuput. It is a liquid, boiling at 75°.

BUTYRIC ETHER. — See “ Ethjd Butju'ate.”

CABRIUVA WOOD OIL. — Myrocarims fasiigiatus is a
member of the natural order Leguminosce, a native of Brazil.

It is know'n locally as cahriuva. The flowers are yellowish-white
and of great fragrance. Their odour resembles that of a mixture
of vaniUa and frankincense or tolu balsam. The wood is highly
valued in Brazil.

Schimmel c& Go. {Report, April, 1896, 64) examined the oil,
and found it to have a specific gravity 0-9283, and optical rotation
— 8° 29'.

CABUREIBA BALSAM OIL. — Myrocarpiis frojidosus and
M. fastigiaius (see also “ Cabriuva Wood Oil ”), both natives of
Brazil, and belonging to the natural order Leguminosce, yield a
balsam from natural as weU as from artificially produced woimds.
The balsam is reddish-brovoi, and greatly resembles Peru and
tolu balsams, both in appearance, consistency and odour. It
contains benzoic acid, both free and combined in the form of
esters. Vanillin is also present in traces.

CADE, OIL OF. — See ” Cadinene.”

FERFU ME RT

CADINENE. — ^This sesquiterpene is found principally in oil of
cade, the product of the destructive distillation of the wood of
Jiniipcnis oxiiccdrus. From the tar so produced, a refined oil can
be obtained by steam distillation. Tliis is a dark yellow viscid
liquid of specific gra%dt\'' O-Olo to 0'930, and optical rotation
about — 30®. It contains much cadinenc, CigHoj, a liquid of
specific gravity 0'921 ; optical rotation, — 105° ; refractive
index, 1-5065 : and boiling point, 273° to 275°. Cadinene yields
a fine blue colour when a few drops are dissolved in chloroform
and the liquid shaken vith a few drops of concentrated sulphuric
acid. It is present in numerous essential oils, including patchouli,
cedar wood. West Indian sandalwood, and others. It is used in
small amount in perfumery, and has been recommended as a
constituent of artificial ylang-ylang oUs.

CALAMINE. — Calamine is essentially zme carbonate, and is
used in the preparation of dusting powders and face lotions.
Originally the term calamine indicated the natural mineral very
finely powdered. It is a hemy powder of a brownish to pinlc
colour, consisting of zinc carbonate, uith varying quantities of
zinc silicate and traces of iron oxide as impurities. To-day the
calamine of commerce is usually artificially precipitated zinc
carbonate, with varying proportions of zinc oxide and traces of
ferric oxide to colotu it. The only important feature for the
perfumer is that it should be finely powdered, free from gritty
particles, and should consist almost entirely of zinc carbonate,
ZnCOs, and be soluble in hydrocliloric acid with the exception of
a small amount — ^not more than 3 to 5 per cent, in the best
samples.

CALAMINTHA OILS . — Galamintlia nepela {Sakireja Cala-
mintha) is a plant flourishing in Calabria and Sieily, and from
which the essential oil has been distilled. The plant is known as
“ false mint,” or “ nepitella.” Sicihan plants examined by Roiire-
Berlrand Fils {Bulletin, October, 1912, 68) yielded 0-14 per cent,
of essential oil. Umney and Bennett also examined a Sicilian
oil {Chemist and Druggist, 67, 970). The figures obtained for these
two samples were as follows : —

Eoure-Bortrand

Specific gravity . 0-925

Optical rotation . -{- 17° 48'

Esters . . . 4-4 per cent

Alcohols (as menthol) 14 „

Ketones . . .20 „

Umney.

0.922
-t- 14®

4-2 per cent.

18-2

10-8

115

8 — 2

PEJRFU MERY

La Face has recentlj’’ examined authentic samples of this oil,
and found quite similar figures, although a sample of French grown
oil is reported as having a specific gravity 0*982 ; optical rotation,
+ 3° 6' ; and refractive index, 1*5115 {La Parfumerie Moderne,
1923, 162).

Galamintha wnhrosa grows wild in certain localities in Travan-
core, and is known locally as JcarimiJmmha. K. L. Moudgill
{Jour. Soc. Ghem. hid.. May 23rd, 1924) distilled a quantity of
fresh leaves with steam, when a 0*35 per cent, yield, calculated
on the dry leaves, of a light j^'cllow oil possessing a strong rather
complex, but not unpleasant odour, was obtained. The oil had
the follovdng characters : d^, 0*8854 ; — 1-4760 ; =

— 45*2° ; acid value, 0*5 ; ester value, 15*9 ; ester value after
acetylation, 40*7 ; aldeh3’-des by the neutral sulphite method,
6*5 per cent. The oil was insoluble in 80 per cent, alcohol, sparingly
soluble in 85 per cent, alcohol, soluble in 90 per cent, alcohol.
In view of the low density and refractive index of the oil, the
difficulty with which it dissolves, even in 85 per cent, alcohol,-
and the ester values, it would apjoear to consist mainly of hj^dro-.
carbons. The oil dried over anhj^drous sodium suljDliate was
distilled under reduced pressure, first over a boiling-water bath
(fractions 1 to 3), and then rapidly over a free flame, and the
following fractions Avere obtained : —

No.

Boiling point.

Pressure.

mm.

Yield
per cent.

To 80°

1*4687

- 62*5°

80°-85°

1*4665

- 68*3°

Above 85°

1-4695

— 53-8°

105°-110° .

1*4900

— 5*2°

Residue and loss

(by diff.) . ■ .

—

Fractions 1, 2 and 3 would appear to contain the same com-
pound. Fractions 1 and 2 were mixed and distilled repeatedly
over sodium under atmospheric pressure, and finally 12 c.c. of
a colourless oil were obtained, of boiling point 176° to 177° ;
d~s; 0*8565 ; = 1*4700 ; = —73*35°. Z-Limonene has

boiling point 175° to 176° ; d, 0*8472 ; — 1*4746 ; =■

— 105°. Bromination of the oil yielded a halogen derivative
which proved to be Z-limonene tetrabromide. In spite of repeated

116

PERFU MEB 3'

fractionation and distillation orer sodium, the /-limonene separated
from this oil \^’as heavier, but had a higher refractive index
than pure Z-limonene, probably due to the presence of small
ouautities of another hydrocarbon, which, however, could not be
separated.

Fra^'iion 4. — ^The aldehyde content of this fraction was found
bj' the sodium bisulphite method to be 10 per cent. The residual
oil had == 1.4930 ; = -}- 5-4° ; d%, 0-9293. It was

soluble in 3-4 volumes of 75 per cent, alcohol.

CALYCANTHUS OIL. — ^Thc air-dried stems of Cahjeanthus
floridus 3 'ield a small quantity of an odorous essential oil, which
has been examined b}* Miller, Taylor and Eskew {Jour. Amer.
Chem. Soc., 36, 2182). Pinenc, cineol, bornyl acetate and other
esters are present in the oil, and probablj’- linalol and sesqui-
terpenes. Tlrrce samples had the following characters : —

Yield ....

0'63 per cent.

0-25 per cent.

0‘39 per cent.

Specific gravity at 25° .

0-9209

0-916]

0-9136

Optical rotation .

-f 2-85°

4-2-84°

4-6-6°

Eefractive index at 26° .

1-4675

1-4713

1-4753

Saponification value

12-5

14-4

; 16-6

Saponification value after
acet}’lation

75-1

65-7

Total alcohols, as borneol

18-41 per cent.

—

' 14-46 per rent.

Enters, as bornyl acetate

4-37 .,

5*04 per cent.

5-81 „

Cineol ....

|70

CAMPHOR AND CAMPHOR OIL. — Camphor is a con-
stituent of numerous essential oils used in perfumery, but, as such,
is only used in the industry for the preijaration of such substances
as camphor ice, etc. Camphor oil, however is of great importance
as the source of supply of a very i.npori;ant raw -uaterial of the
perfume industry, namelj’’, safrol (g'.r’.). The tree yi.elding camphor
oil is Ginnamomum campliora. It is widely distributed throughout
the eastern provinces of central China, on the island of Hainan,
and very extensively in Formosa. It also occurs as a forest tree
on the islands of Kliusliiu and Shikoku. The greater part of the
camphor produced comes from Formosa, and the industry is
practically a Government monopoly. The tree is felled and the
young branches and twigs are chopped up and placed in perforated

117

PERFUMERY

jars and heated over steam. The steam satiirates the fragments,
and the crude camphor sublimes into earthenware pots placed
over the jars. The crude material is pressed and separated into
a slightly more refined camphor, and a certain amount of camphor
oil. The greater part of the camphor oil of commerce is, however,
obtained by direct distillation of the chips in crude stills. The
oil is drained from the separated camphor, but still retains
a considerable amount in solution. Kedistillation is resorted
to until it does not pay to separate the camphor any further.
So that, in fact, solid camphor is really o:^y a fraction of
the entire camphor oil,” and the camphor oil of commerce
is really only the residual fractions after the extraction of most
of the camphor.

Camphor, HjgO, is the ketone of the alcohol borneol (g'.u.),
and occurs in the essential oil as fZc.rb-o-camphor, the rare Icevo-
camphor being found in the oil of Matricaria 'parllicnixim. It forms
a translucent mass, obtainable in coarse powder by subhmation,
of specific gravity 0-985 ; melting point, 176° to 179° ; boiling
point, 205° to 207°; and specific rotation, 44°. It is freely
soluble in organic solvents (alcohol, 1 in 1 ; chloroform, 4 in 1 ;
ether, 2 in 1). It occm's in commerce in coarse powder (fiowers
of camphor), in bell-shaped masses (beU camphor), or in small
tablets of varying sizes. In the semi-refined condition it is also
imported in the form of large slabs. ■

The crude camphor oils of commerce exist in, roughly, four
different varieties. These are as follows : —

(1) The crude oil as it leaves the distillery, -with as much
camphor separated as possible. This has a specific gravitv 0-950
to 0-998.

(2) Heavy camphor oil, or brovm camphor oil, which is the crude
oil from which the low-boiling terpene fractions have been as
completely removed as possible. This oil is rich in safrol. Specific
gravity, 1-000 to 1-040.

(3) The light oil, consisting of the terpene fraction mentioned
under (2). Specific gravity, 0-870 to 0-890.

(4) The very high-boiling fractions, extremely rich in safrol,
of specific gravity 1-060 to 1-075, and which is sold as/‘ artificial
sassafras oil.”

Safrol, obtained from camphor oil, is the raw material from
which heliotropin is manufactured.

A very large number of patents have been granted for the
manufacture of camphor artificially. A clear . distinction must

118

PEBFU MEET

be made between tlie true artificial camphor, the so-called
“ p\-nthetic camphor,” and pinene hydrochloride. Cm HmHCl,a
crj'stalline compound of pinene which was knowm as artificial
camphor, on account of its physical resemblance to true camphor,
before the artificial production of camphor had been achieved.
This so-called artificial camphor is prepared b}’- passing a current
of dry hvdrochloric acid gas thi’ough well-coolcd pinene. The
resulting crystals melt at 127°, and have a camphoraceous odour,
and may be used as a substit/utc for camphor to a certain extent.
A complete sj-nthesis of camphor has been achieved by Komppa
{BcricMc, 36,' 1332), but has no commercial application. Jlany
processes jdeld camphor on a reasonably paj'able scale, but,
owing to tlie fact that the Japanese monopoly is able to control
prices, artificial camphor is rarely able to compete with the
natural substance. In general, such processes for the production
of artificial camphor depend on the conversion of pinene, obtained
from turpentine oil, into pinene hj'drochloride, which, bj’’ abstrac-
tion of hydrochloric acid, jdelds camphene. This is converted
into isobornjd acetate bj' treatment with acetic and sulphuric
acids, and is saponified by treatment with allcali, and the resulting
isoborneol is oxidised to camphor.

(See also “ Sho-Gjm and Yu-Ju Oils ” ; refer B. J. Eaton,
Dejyt. of Agricvllwc, Federated Malay Stales, Bull. 15, February,
1912, for attempts at cultivation of camphor trees in Malay
States ; and see photographs of stills by Monopoly Bureau of
Formosa, reproduced in Parry, “The Chemistry of Essential
Oils,” 4th ed., vol. ii., pp. 158, 159. For the liigh-boiling sesqui-
terpene compounds of camphor oil, see Ruzicka and Stoll, Helv.
GMm. Act., 1924, 7, 260.)

CANANGA OIL.— Oil of cananga and oil of ylang-ylang are
obtained from the same botanical source, the superiorit}’’ of the
ylang-ylang oil being due to the different conditions under wliich
the trees grow, and to the methods of distillation. The tree from
wliich the flowers are distilled is Cananga, odorala, one of the
Anonaeeoi, of which a native name is Alan-guilan, or Ililang-
Ihlang, meaning the “ flower of flowers.”

The tree is a native of Ava and Tenasserim, and is generally
distributed and cultivated throughout southern Asia. It attains
a height of about 60 feet. The flowers are very handsome and
conspicuous, bell shaped, of a pale yellow or greenish colour, with
a beautiful perfume, often compared with a mixture of hyacinth,
na»’cissus, clove, jasmin and lilac.

- 119

PEEFTJ M EB.7

The following account of the plant is from the Perfumery and

Essential Oil Eecord, 1910, 223 ; , , r; 4 .

“ The plant from which it is derived, Cananga odorata, was farst

described by Enmph in 1750 under its Malayan designation of
Bonga cananga. It is called Isjampa by the Javanese. It is
stated to have been first introduced into India from Sumatra m
1797 a description of it in the Botanical Gardens of Calcutta
being by Boxbm’gh (‘ Flora Indica,’ 1832). It is described by
Hooker and Thompson (‘ Flora Hidica,’ 1855). It is lUustrated in
the ‘ Flora Java ’ by Blume (1829). We arc courteously informed
by IMr. Prain, the director of the Hoyal Botanical Gardens at
Kew, that no flowering plants are avafiable for photography at
the present time. Fluckiger (Pharm. Jour., May 14th, 1881)
stated that the incorrect name Unona odoraiissima so ^dnscribed
from its overpowering odom’ — originated vdth Blanco ( Flora de
Filipinas,’ Manila, 1845), and for years the oil was described in

price lists as oleum unoiiffi. ^ ■ .or a

'' The oil appears to have been sent to Europe first m 1864:,
when it was offered in Paris. The first shipments were not made
from klanila, but the recognition of its beautiful odour resulted
m its distillation in Manila, at first by German pharmacists.

“ Cananga odorata attains a height of 60 feet, has few, but much
ramified, branches, and handsome tea-shaped flowers, which droop
elegantly. The blossoms grow in every month of the year, but
contam most oil in the months of June to December. The tree is
common to many localities, but is found principally in weU-
populated districts, where it appears to thiive best. The reason
for this has not been definitely ascertained, but it appears to be
accurate and constant. It is propagated by planting seedlings
or cuttings about 20 feet apart, which grow very rapidly, fiowermg

in the tliird year. ■ . . t ^

“ In Manila the petals are subjected to the simplest form

of distillation, the oil being divided into two or more portions,
the first clear and delightfully fragrant, the later distillate
yellowish and frequently empyreumatic. It is stated that,
to obtain a prime quality of essence, 300_to 350 1b. of flowers
would be needed as to season and maturity of flowers to yield

1 lb. of the oil. i t 1 ;+

“ The Java oil distillation has been described by De Jong after

an official visit of mspection to Serang. The petals are stated
to have been pounded before distiUation, the resulting oil contain-
ing more sesquiterpenes, and being less fragrant than the Manila

120

PERFUMERY

oil. The methods of distillation have been much improved, vith
a corresponding improvement in the oil.

“ In the distillation in Keunion no separation of the oil was
made until recently, the idea being to obtain a high percentage
3 'ield rather than delicacy of odour, and, according to figures
communicated to us, the yield is freq^uently as high as 2 per cent.

“ The distinction between cananga oil and 3 dang- 3 dang oil is
not sharply defined. The former usually consists of the higher
fractions containing a greater proportion of sesquiterpene, but in
some districts the entire oil is sold as cananga oil.

“Ylang-jdang oil is the finest grade, consisting of the first
fractions of the oil, and containing a greater proportion of
ox 3 ’'genated constituents.”

The cultivation of the tree reaches its maximum degree of
perfection in the Plulippine Islands, the finest oil being distilled
in Manila. A considerable amount is also distilled in the island
of Reunion, and a good deal of oil of less fine quality comes from
Java and the neighbourhood. Commercially, the oil distilled in
the Philippines is ylang-jdang oil par excellence. The oil from
Reunion is usually termed ylang-ylang, but is not of such fine
odour as the Manila oil ; whilst the Java oil is known as
cananga oil.

As there has been much confusion over this oil, the following
account of it, due to R. P. Bacon {PMlipp. Jour. Sc., 3, 108, 65),
vdU be of interest : —

In Manila, where the conveniences for careful distillation are
greater than in outlying districts, fine oils as well as second-class
oils — ^v'hich are frequently known even there as cananga oil —
are produced, but in the provinces the distillers, who are com-
pelled to work with less scientific apparatus, generally produce
only a second-class oil. Quite three-fourths of the blossoms
delivered at Manila are green and unripe, although it is of the
highest importance to use the ripe yellow blossoms for the best
quantity and yield of oil. There has been much mystery made
over alleged trade secrets connected with the distillation of this
oil, but Bacon does not consider any such secrets exist. The
great mistake distillers make in the provmces is burnhrg the
'flowers in the still and wrongly selecting the fractions of the oil
distilled. They attempt to get 1 kg. of oil from 150 to 200 kg.
of flowers m one bulking, whereas they should only obtain 1 kg.
of the finest oil from 400 kg. of flowers, and then about the same
quality of second grade oil. The industry is also an important

121

PERFUMERY

one in BeTinion, and here again it has been shown that by a
short-time distillation the smaller amount of oil is compensated
by the fine quality.

Small quantities of the oil are produced in Madagascar and in
the Seychelles Islands.

The climatic and soil conditions, coupled with the considerations
above noted, account for the difference in the quality of the various
oils. Bacon has examined a number of' Pliilippine oils, and gives
the following figures : —

Second quality.

First qualit3L

Specific gravit 3 ’' at 30° /4° .

0*911-0*958

0*896-0*942

Refractive index at 30°

1*4747-1*4940

1-4788-1-5082

Optical rotation

- 27° to - 49*7°

- 27*4° to - 87°

Ester number .

90-138

(in one case 169)

42-94

Bacon classifies the oils as follows. First-class oils usually have
an ester number over 100, a refractive index not above 1*4900,
and optical rotation rarely over — 45°. Low values for optical
rotation and ester number usually indicate low-grade oils.

The usual analytical values for Reunion and Java oils are as
follows : —

Founion.

Java.

Specific gravity at 15°

0*930-0*967

0*906-0*956

Optical rotation

- 34° to - 65°

— 15° to — 52°

Ester number

96 to 160

10 to 60

Refractive index at 20°

1*5000 to 1*5100

1*4900 to 1*5050

Artificial 3 dang- 3 dang oil is a commercial product. The principal
bodies used in its preparation are ^jara-cresol meth 3 d ether, linalol,
geraniol, isoeugenol, benzyl acetate, benz 3 d benzoate, isoeugenol
meth 3 d ether, methyl benzoate, benzyl alcohol, and methyl
anthranilate.

Adulteration of 3 dang- 3 dang or cananga oils vdth benz 3 d
benzoate is a question of considerable difficulty to the analyst,
as benz 3 d benzoate is, in certain proportions, a natural constituent
of the oil. J. C. Umney (P. cC? E. 0. R:, 1914, 37-86) gives the

122

PERFUMERY

folloT\’iiig figures for a number of samples of various origins wliicli
he examined : —

Manila.

1 Bourbon,

Specific gravity , . 1

0-927-0-969

0-964-0-967

Optical rotation

— 38° to — 51°

— 39° to — 41°

Refractive index . . :

1-494-1-505

1-5130

Ester number

99-153

143-160

Non-volatile residue (on
water bath, in 2 hours) .

4-3-1 6-4 jier cent.

25-1-40-3 per cent.

iMadagascar,

Slayotle.

Specific gravity

0-961-0-981

0-947

Optical rotation

- 30° to - 42°

— 48°

Refractive index

1-5112

1-5007

Ester number

123-171

115

Non-volatile residue (on
water bath, in 2 hours) .

16-9-29-3 percent.

14-19 per cenl .

If, however, the oil is heated on a water bath until no further
loss in weight is noted, any non-volatile residue over 7 per cent,
should be regarded with suspicion. Further, the non-volatile
residue should be saponified, and if the saponification value varies
outside the limits 65 to 100, the oil is probably adulterated. If
fatty oils have been used as adulterants, the saponification value
will be much higher, and the residue must be examined for fatty
acids, which can be separated and their molecular weight deter-
mined, which win indicate the origin of the adulterant.

Umney found that in the case of the finest Manila oils the
residue does not usually exceed 6 per cent., although inferior oils
contain more than this. The evaporation on the water bath should
be continued for at least eighteen hours, as benzyl benzoate is
very slowly volatilised at water-bath temperature.

Roure-Berlrand Fils {BvMetin, April, 1910, 61) give the table
on p. 124 as typical figures for various ylang-ylang oils.

The foUoAving references are to important papers on the oil,
where further details may be found : —

(1) ” East African lhang-Ylang Oil ” {SchimmeVs Report,
October, 1911, 102).

123

PERFUMER I

Nossi-Be.

0-9673

— 42° 12'

1 voL, then
cloudy.

1-4
129-5
45-3

per cent.

154-7

42-7

per cent,

35-6

per cent.

7-1

per cent.

(2) “ Reunion, Nossi-Be, Mayotte, and Manila Oils ” {Roure-
Berirand Fils, Bulletin, April, 1910, Gl, and October, 1911, 40).

(3) “ Sej^clielles Ylang-Ylang Oil ” {Bulletin of the Imperial
Institute, per “ The Clieinistry of Essential Oils ” (E. J. Parry),
4tli ed., vol. i., p. 520),

CANARIUM RESINS. — ^Tlierc are a number of resins or
oleoresins known under the name elemi. hlost of these are the
product of Canarmm species, but the resinous matter most
commonly known as elemi is the substance collected in the
Phihppine Islands, principally from Ganarivm luzonicuni, and
possibly from G. commune. TJiis is kno^vn in commerce as Manila
elemi. It contains from 15 to 30 per cent, of essential oil of
some perfume value. The oleoresin is used as a fixative, but should
be used in the form of an alcoholic tinctm’e from which the
insoluble matter has been rejected by filtration. When fresh,
Manila elemi is pale yeUow in colour, soft and granular, somewhat
resembling crystallised honey in appearance. The general
characters of the oleoresin vary 'svith the district m which it has
been produced, the soft and hard varieties having the foUovdng
characters : —

Soft. Hard.

Volatile oil . 15-30 j)er cent. ., 8-9 per cent.

Ash . . 0-02-0-2 „ . 0-2-1

Acid value . 17-25 . . 15-28

Ester value . 7—25 . . 25-28

Reunion.

Specific gravity at 15° 0. 0-9492

Rotatory power . — 38° 8'

Solubility in 90 per/ 4 vol., then
cent, alcohol . \ cloudy.

Acid value . . —

Saponification value . 96-03

Esters, as linalyl J 33-6

acetate . . ( per cent.

Saponification value \ jsg.H

of the acetylated oil J

Total alcohols (as ( 40-3

linalol) . . I percent.

Combined alcohols {

( per cent.

fill ( 13*9

Free alcohols . - cent.

Mayotte.

Manila.

0-9324

/0-911 to

\ 0'958

— 47° 40'

1 vol., then

1—27° to
( — 49-7°

cloudy.

/ “

1-0

—

113-4

90 to 138

39-7

per cent.

} -

134-4

—

41-0

per cent.

)

31-2

24-7 to 38

per cent.

9-8

per cent.

/ “

124

PERFUMERY

Tlie essential oil is a fragrant liquid recalling the odour of mace,
and having the folldudng characters : specific gravit3^ 0-870 to
0-915 ; optical rotation, + 30° to + 55°, but rarelj^ + 4° to
134° ; refractive index, 1-4775 to 1-4900 ; acid value, 0 to 2 ;
and ester value, 4 to 10. The oil is very variable in composition.
The foUoving constituents have been detected in twenty-one
.samples examined by Clover (Amer. Ghem. Jour., 1908, 39, 613) :
limonene, phellandrene, pinene, terpinene, and terpinolene. A
sesquiterpene alcohol, elemol {q-v.), is also present, and a small
amount of a phenol ether which has been named elemicin.

CARAWAY OIL. — This oil is obtained by the distfilation of
caraway fruits, the product of Cariim carui, a plant found in
northern and central Europe. It is erdtivated in various countries,
especially in Holland. The name caraway and the Spanish name
alcaraliueya. are derived from the Arab Icarawya. The fruits
yield from 3 to 7 per cent, of essential oil having the following
characters : specific gravity, 0-907 to 0-918 ; optical rotation,
70° to -f 83° ; refractive index, 1-4840 to 1-4890 ; and contain-
ing 60 to 60 per cent, of carvone.

Caraway oil consists almost entirely of carvone (carvol),
Cio H14O, and the terpene limonene. Its value depends on the
carvone, so that it may be approximately valued by its specific
gravity, that of carvone being 0-964, and that of hmonene 0-848.

The best method for the determination of carvone is the neutral
sulphite method {vide “ Aldehydes, Determination of ”). If the
oil be fractionally distilled, not more than about 25 per cent,
should distil below 180°, and from 55 to 65 per cent, should distil
above 200°.

On the Continent pure carvone is largely employed in place of
caraway oil. Hence there is a considerable amount of caraway
oil available from which much of the carvone has been abstracted.
Some of these oils are standardised to the lowest limits that the
various pharmacopoeias give for the oil ; others have so much
carvone abstracted that they can only be sold as “ light ” caraway
oil or, in common with the oil distilled from the chaff and dust
left after tlireshing the seed, as “ caraway chaff ” oil. These
light oils are employed in cheap soap perfumery. A stfil lower
grade o'il is sometimes sold under the name “ carvene.” This is
merely impure limonene with a slight caraway odour, and consists
substantially of the terpenes of caraway oil.

CARDAMOM OIL. — ^Traces of cardamom oil are sometimes
used in eau de Cologne and in artificial lily perfumes. The

125

PE RFU M EBY

ordinaiy cardamom is the fruit of Eleitaria cardamonium, one of
the Zingiheracem, Although the plant grows wild in the forests
of southern India, where it is commonly known as hachi, the bulk
of the fruits of commerce are provided by cultivated plants, and
Ceylon supj)lies the greater part of the cardamoms used. Some
of the cardamoms met with are the product of one or more
varieties of the plant, and yield essential oils which differ between
themselves. The writer (E. J. P.) has distilled the oil from the
so-called Ceylon-Malabar and the Ceylon-Mysore seeds. The
former jdelded 1'3 jDer cent., and the latter 2*6 per cent., of essential
oil. The odours of the two oils were practicaUj’’ indistinguishable.
The folloAving figures cover those of most pure samples : specific
gravity, 0-923 to 0-945 ; optical rotation, -f 24° to -}- 48° ;
refractive index, 1-4620 to 1-4675 ; and ester value, 90 to 150.

The oil contains terphtyl acetate, terpmeol, and limonene.

(See also E. J. Parry, “ The Chemistry of Essential Oils,” 4th ed.,

vol. i., J)- 101 ; Sawer's “ Odorographia,” 2nd series, jd. Ill ;

and Eidle}’-, “ Spices,” p. 324.)

CARNATION. — Tlie carnation is merely a varietj’ of the

clove pink Dianihvs cargogjliyllvs, the species including carnations,
pinks and picotees. The rich odour of the less highty cultivated
varieties of the clove and carnation has alwa 3 ’’s been exceedingl}’"
popular. In the more higlily cultivated flowers perfume has given
wa}'^ to form and colour, as in the case of the rose. A certain
amount of the natural perfume is extracted in the south of France,
principally in the form of a pomade, although a little concrete or
absolute reaches the market. The buUc of the carnation perfume,
however, is based on synthetics, rounded off with natural flower
perfumes and fixatives. According to a writer (anonymous) in
the Perfumery ami Essential Oil Record, 1917, 18, nearly all the
species of Dianilms are natives of Em’ope, tropical Asia, and
northern Africa. In France, where it is knovm as (Eillet, it is
largely cultivated for decorative purposes. It is a beautiful plant,
remarkable not onl}^ for its perfume, but for the colour and
elegance of its flowers. Some 2,000 varieties have been produced
by cultivation, of which the following may be mentioned ;
Alegatiere (vivid red flowers), Antoine Devert (cerise coloured),
Commandant Riviere, Comtesse de Paris (yellow’^), Fran 5 ois
Buchner (bright red). General Boulanger (vivid red), Hugues
(abundant red flowers), Jean Sisley (red and yellow). La Fontaine
(yellow, striated), L^on Aurange (bright cerise), Madeleine Solignac
(lilac rose), Mahonais (flesh coloured, flourishing in winter and

126

PERFUMER 1

earij spring, cultivated round Toulon), Enfant de Mce (red or
vliite flowers), Pauline Borriglione (rose or salmon pink). President
Carnot (purple flowers). Rose Bivoire (rose coloured). Souvenir de
Pifine Llari (wdiito flowers), and Souvenir de Madame Gobet
(yellowisli copper coloured).

Other varieties which flomish in winter are Auguste Vernier,
Capitame Berner, Laverriere, hladame de Presle, Oriflamme,
Raphael, and Roi des Rouges.

C^dlivatwn . — Carnations flourish best in a w’ell-di-ained soil
vith free access of air and sheltered from the sun. Thej’' are
reared from seed, and from layers or suckers. Seeds are sown in
autumn or spring in earthenware pans or pots. AVlien sovti from
March to May, the young plants may be planted out about
fourteen months afterwards, when they possess five or sis: leaves,
care being taken to protect them from the sun’s raj^s and from
cold and damp. To obtain autumn or winter flowers, the seeds
are sown in autumn. Slips should be planted in a light sandy
soil in pots, leafy branches being preferable for this operation.
The slips will root in thirty to forty days. Layering is effected
by embedding the branches near a node, after making a sma.I]
longitudinal incision before burjdng them. This favours the
development of roots. The branches are kept in place by means
of small pieces of wood. Durmg the summer the extremities of
branches which tend to lengthen are pinched, in order to render
the plant more vigorous and retard flowering. Erom time to
time lic[uid .manure should be applied to obtain a greater
abrmdance of flowers.

A clove-scented perfume is also developed in the flowers of a
convolvulus found in the forests of Mednapore, in Bengal, which
is botanically knovu as Letlsonia hona-nox (Roxburgh). The
flowers are large and white, expanding at sunset and withering
at sunrise ; they are produced during the rainy season.

Another clove-scented convolvulus is the Iponicea grandiflora
(Roxbm-gh), knovm in Bengal as Doodiya-Kulmi. This plant
twines. to a height of 20 feet, and bears white flowers 4 to 6 inches
in diameter. It is common in hedges in Samulcota and on the
banks of watercom’ses. It is closely allied to the Lettsonia hona-nox.

A clove odour is strongly developed in the bark of Laurus
culilawan {Laurus Carophyllata), and in Cinnamomum sinfox. The
bark of Cimiamomum culilawan, a native of Amboyna, is called
“ clove bark ” oh account of its strong odour of cloves. “ Clove
cassia ” is the name applied to the bark of Dicypcllium Garyophyl-

127

PEBFUM EE Y

latum, wliicli is also known as Brazilian clove bark. It is found in
Para and Bio Negro. The Madagascar clove nutmeg is the fruit
of Agatliophyllum aromaiicum, a laurel the leaves of which are
used the natives as a condiment.

The actual basic material for artificial carnation is isoeugenol
iq.v.), usually mixed vdth some eugenol. Hexyl-methyl ketone,
isobutyl-phenyl acetate, benzyl acetate, phenyl-acetic aldehyde,
and terpineol are also often employed in judiciously small amount,
with a Httle benzyl isoeugenol as a useful fixative. A useful
variation in “ shade ” of the odour is produced by the use of a
httle methyl eugenol and methyl isoeugenol.

The essential oil of the carnation has recently been examined
by Ghchitch {Bull. Soc. Chim., 1924, iv., 35, 205). The yield is
only about 0-003 per cent, calculated on the fresh flowers. The
oil is a pale green sohd of intense odour, which, until heavily
diluted, does not resemble the odour of the flower. It melts at
35° to 37°, and has a specific gravity 0-869 at 40° ; optical
rotation, — 8 ° 28' ; acid number, 4-9 ; ester number, 61-3. It
contains 31 per cent, of a stearoptene, which is probably hepta-
cosane, C 27 H 5 Q, melting at 53° to 54°. Traces of an aldehj^de are
also present.

CARROT, OIL OF.— See “ Daucus, Ofi of.”

GARVAGROL. — ^This body is a phenol, of the formula
C 10 HJ 4 O, isomeric with thymol. ChemicaUy it is isopropyl-ori/jo-
cresol. It is fomid, frequently in association with thjunol, in
various thjune and origanum oils. It also results artificially from
the treatment of carvone by potash. It is a colourless oh of
fragrant, refreshing odour, sohdifying at about 1°, boiling at 236°,
of specific gravity 0-981, and refractive index T5240.

CARVENE.— See “ Caraway Oil.”

CARVONE. — Carvone, C 10 H 14 O, is a ketone, the characteristic
odour bearer in oils of caraway and dill, in which it occurs as
cZea-fro-carvone. It is found as ZcEvo-carvone in kuromoji oil. It
is an odorous liquid of specific gravity 0-964 ; optical rotation,
-f 59° 30' ; refractive index, 1-5020 ; and boiling point, 224°.

GARYOPHYLLENE. — ^This body is a sesquiterj)ene, C 15 H 24 ,
occurring in oil of cloves and several other essential oils. There
are several isomeric bodies known under this name which are
of considerable interest to the chemist. But from the perfumer’s
point of view the mixture of sesquiterpenes obtained from oil

12 s

PEJRF U3IEn Y

of (Aorc^ ^vhoii ilic cugenol lias been almost complctel}^ extracted
h' Lnov.’ii as carvopliyllcnc. This mixture has a specific gra\ity
from 0-P05 to 0'910 ; optical rotation, — 7° to — 9"^ ; refractive
iivlex. about l-oOlO : and boiling point, about 258° to 2G1°, With
a little cuacnol left in the mixture, it is the light clove oil sold
for clicap soap perfumery.

CASCARILLA. — The ca^onrilla bar!: of commerce is tlie bark
of C/'o!o?i Elciflcvif'ij and possibly" that of Crofoit CcisccivUlci, Tlic
lives arc indigenous to the Rahama Islands. The bark has a
pleasant aromatic odour and burns with an exceedingly fine
fragrance, so that it often used in fumigating or incense compo-
sitions. It yields from 1 to 3 per cent, of essential oil, which is
occasionally used in jicrfuniery, and wliich has the following
characters': specific gravit3% 0-895 to 0-92S ; optical rotation,
+ r to d- 12°; refractive" index, 1-4910 to 1-49G0 ; and ester
number, G5 to 75. The perfume constituents have not been
identified, but it contains a scscjuilcrpcne alcohol, C15H0.JO, and
an acid isomeric with undccjdcnic acid.

CASSIA OIL.— Cassia oil is the distillate from the leaves,
twigs, and other portions of Cimunnoimnn cassia, the so-called
Chinese cinnamon, which is probably a native of Cochin China.
It is chiefiy cultivated in China proper, the three principal districts
being /laiwu in the Kwangsi province, Lupko, and Loting in
the Kwangtung province. In a report on a journe}- to Kwangsi
by H. Scliroelcr in 1897, the wnter staled that the shrubs destined
for the production of the Cassia lignea, as the prepared bark is
tenned, are partly stripped during the summer months of their
smaller branches and their juic^^ leaves. These are then boiled
in large vessels, and the cassia oil recovered 133" a primitive S3'’stcni
of distillation. An interesting account of the origm of tlic oil is
contained in a paper in the Jouvnal of the Liniican Soo'icly,
December, 1882. The distilleries are situated in valleys where an
abundant flow of water for condensing purposes is available.
If leaves only are used for distillation, the oil is of the finest
quality, so that, as a rule, only about 30 per cent, of twigs are
used vdth 70 per cent, of leaves. A typical oil so distilled was
found by Niedliardt to contain 8G per cent, of cinnamic aldeh3^de,
the principal odorous constituent of the oil. A specimen distilled
entirely from the bud sticks was found by ScMinmcl cO Co. to
contain 92 per cent, of cinnamic aldeb3’'de, and the following
results “were obtained from various -parts of the plant : (1) Cassia

r. 129 0

PERFUMER Y

bark : yield, 1-5 per cent. ; specific gravity, 1-035 ; cinnamic
aldeli3^de in the oil, 89 per cent, (2) Cassia buds : yield, 1-55 per
cent. ; specific gravity, 1*026 ; cimiamic aldehyde in the oil,
80-4 per cent. (3) Cassia bud sticks : yield, 1-64 per cent. ;
specific gravity, 1-046 ; cinnamic aldehj^de in the oil, 92 per cent.
(4) Cassia leaves, stalks, and twigs : yield, 0-77 per cent. ; specific
gravity, 1-055 ; cinnamic aldehyde in the ofi., 93 per cent.

Cassia oil is imported chiefly from Hong Kong in “ leads ” —
leaden vessels holding 16| lb. of the oil. It is invariably sold
graded on its cimiamic aldehj'^de content, viz., 70 to 75 per cent,,
75 to 80 per cent., 80 to 85 per cent., and 85 to 90 per cent., the
usual quahty being 75 to 80 per cent. The lower grades are
almost invariably adulterated, usually with rosin, pure oils rarely
containing less than 85 per cent, of cinnamic aldehyde. A pure
oil (?.e., as distinguished from the oils which may be said to be
standardised down more or less honestty) has the following
characters : —

Specific gravitj’’
Refractive index .
Optica] rotation
Acid value .
Cinnamic aldehyde

1-055-1-072
1-6000-1-6060
— r to + 6°

6-20

Not below 83 per cent.

A pure oil is soluble in 2 volumes of 80 per cent, alcohol. Nearly
all adulterants interfere with tliis character. Ordinaiy rosin, or
coloplionjq the most usual adulterant, can be detected, firstly, by
a much increased acid value, as colophonj’’ consists almost entirely
of resin acids or anhydrides ; secondly, bj^ adding a few drops
of a saturated alcoholic solution of acetate of lead to a 25 per cent,
solution of the oil in 70 per cent, alcohol. A distinct precipitate
indicates the presence of rosin. An estimation of the amount of
the adiilterant is not usually necessary, as the determination of
the cinnamic aldehyde, upon which the value of the oil practicalty
entirelj^’ depends, is far more acem-ate than anj^ rosin determina-
tion. It can, however, be approximately determined by heating
the oil to 280°, until white fumes are given ofp, when any residue
above 10 per cent, may be regarded as colophony. Cassia oil
attacks the lead of the containers, oudng to the presence of
cinnamic and other acids, Lubetti {Joicr. Soc. OJmn. Ind., 1920,
35) tests for tliis as follows : 5 c.c. of the oil are dissolved in
15 c.c. of 90 per cent, alcohol, and this solution “ Nesslerised ”
against a standard solution of lead acetate in alcohol, with

130

PBRF U ^FER T

sulpliirle of ammonium, using a lead-free cassia oil (redistilled)
in the blank solution. (For the estimation of the cinnamic
aldehyde (g.n.), see under “ Aldehydes, Determination of.”)

Cassia oil closely resembles eimiamon oil in odour, but it is
not nearly so delicate. Apart from cinnamic aldeltyde, the oil
contains a little cinnamic acid, terpenes, the acetic esters of
cinnamic and phenyl-propyl alcohols, or/7m-methyl-coumaric alde-
hyde, salicylic aldehyde, coumarin, and salicylic and benzoic acids.

Ca.~sia oil is used in the perfuming of “ old brown Windsor ”
soap, and in many perfumes where a less delicate odour than that
of the finer cinnamon oil is permissible. Both oils are frequently
replaced by artificial cinnamic aldehyde.

CASSIE.— See » Acacia.”

CASTOR, or castoreum, is an animal perfume material of
considerable value to the perfumer as a fixative. It consists of
the dried membranous follicles of the beaver {Castor fiber), which
are situated between the anus and genital organs of the animal of
both sexes. They are fiUed with a viscid oleoresinous glandular
secretion, which is of disagreeable odour, but which is not noticed
on dilution. The follicles are removed after the animal is killed,
and dried either hj smoke or in the sun. When quite fresh, castor
is a white creamy liquid, but by the time it appears in commerce
it is unctuous and semi-solid. Two varieties are recognised, the
Canadian and the Russian, the latter, however, rarely reaching
tins market. Castor is sold in the form of more or less soft and
unctuous masses which gradually harden, and which are con-
tained in flattened and wrinlrled sacs from 2 to 3 inches long. It
is nauseous as to odour, and of a bitter taste. So far as London
is concerned, castor comes on to the open market only once a
year, as it is almost a monopoly of the Hudson’s Bay Companjy
who offer the year’s collection at an amiual sale, the amount
ofltered being about 1,000 lb.

In addition to its direct use as a fixative, castoreum frequently
enters into the composition of the so-called artificial “ ambers.”

Castor varies considerably in composition, always, however,
containing a small quantity of a highly odorous essential oil. It
contains from 40 to 70 per cent.- of resinous matter soluble in
alcohol, traces of salicin and benzoic acid, and from 4 to 5 per
cent, of a crystalline body • which has been named castorin.
According to Slingard, castor contains 88 per cent, of matter
soluble in ether, and about 8 per cent, of substances volatile at

131 0 —

PERFUMERY

100°. Castor has frequently been described erroneously as the
dried testicles of the beaver.

GEANOTHUS VELUTINUS, OIL OF.— According to
L3Tin, Lee, and Clausen {Jour. Amor. Pliarm. Ass., 1923, 12,
419), the leaves of this i)lant, knorvn in the United States as the
stick}’^ laurel, or mountain balm, jield about 0-1 per cent, of
essential oil having a specific gravity 1-0167 at 25°, and refractive
index 1-5315 at 20°. It is optically inactive. It contains cimiamic
aldehyde, and probabty eugenol. -It has a sweet odour resembling
cinnamon and clove.

CEDAR WOOD OIL. — This essential oil is of considerable
value, mostly for cheap j)erfumery where a heavy odour is
required. It is distilled from the wood of Juniperus virginimia,
the Vngmia cedar, with, possibly, the admixtm-e of other cedar-
woods. Much of it is distilled from the waste shavings obtained
in the American lead pencil factories. The finety powdered wood
burns vnth a highl}’’ aromatic odour, and is used in incense and
similar preparations, and for ceremonial or fumigating pm-poses.
Although a very inexpensive oil, it is useful in high-grade as well
as cheap perfumery, and blends well with odours of the violet
type. The pure oil has a siDecific gravity from 0-940 to 0-9G2,
and optical rotation — 25° to — 47°. The refractive iirdex varies
from 1-5000 to 1-5100. The principal constituent of the oil is the
sesquiterpene cedrene, ; it also contains cedrol, or '' cedar

camphor,” CigHogO, cedrenol, CjgHg.iO, and ^jseiaZo-cedrol,
CigHagO. Cedrol is a ci-j’^stalline bodj’’ of pleasant aromatic odour,
meltmg at 84°.

The Atlas cedar {Cedriis Atlaniica) is also distilled on a small
scale for its oil. This tree is probabty only a variety of the cedar
of Lebanon [Cedrus Lihani). The oil is similar to ordinarj'' cedar
wood oil, but of finer odour. It has a specific gravity 0-950 to

0- 970 ; optical rotation, 45° to + 62° ; and refractive index,

1- 5119 to 1-5175.

Roberts {Jour. Ghem. Soc., 1916, 791) has examined the oil
distilled from Cedrus deodara, the deodar tree, a native of the
western Himalayas, which is widely distributed in northern
India. The oil has a pleasant balsamic odour, and has the follow-
ing characters : specific gravity, 0-956 to 0-976 ; optical rotation,
-f- 34° to -f 62° ; refractive index, 1-5195 to 1-5225 ; and ester
number, 5 to 21. It contains a ketone, which is probably
methyltetrahydroacetophenone. Deodar wood oil has recently

132

PERFU MERY

been examined l)y J. L. Simonsen, D.Sc., and M, G. Eau at tlic
Fore=:t Eesearch Institute, Delira Dun {Indian Forest Records,
0, 123). The oil einploj'cd by them was derived from logs
seventy -five yeans old, which furnished a yield of 2'0 per cent,
of oil.

The pleasant aromatic odour which characterises deodar oil was
stated by Roberts to be probably duo to the presence of from about
2 to 10 per cent, of p-methyltetrahydroacetophcuonc, a compound
not found previoush' in nature. This statement has been con-
firmed b}' the above investigators, who worked with a large
Cjuanlit}’ of the oil, and were thus able to isolate the ketone in a
pure condition, and establish its identity by preparing many of its
derivatives.

The principal constituent of the oil is a sesquiterpene, which is
associated with a sesrpiiterpeno alcohol ; as, however, neither of
these compounds j'ieldcd a crystalline derivative, it was not
possible to characterise them beyond determining their physical
constants. Other constituents which have been isolated from
deodar oil are as follows : a phenol (unidentified) and esters of
butyric or isobut^Tic, hexoic, heptoic, and stearic acids.

Samples of deodar oil were submitted by the Imperial Institute
in 1915 to English and Continental firms of soap makers and
essential oil distillers, who expressed the general opinion that a
market eould probably be found for the oil if it were offered at a
low price. It was stated concerning a sample of oil which the
forest chemist has had valued recently in England, that the oil
might find a small market as a substitute for cedar wood oil in
soap perfumery, but that its value would onl}’^ be 2s. Gd. per pound.
At this price it was not considered that production would be
remunerative.

The suggestion has now been made tliat it might possibly prove
profitable to utilise the oil obtained by the destructive distillation
of the wood as a timber preservative.

A cedar w’ood from East Africa, obtained from Jnniperns
proccra, has been arriving in Europe for some time past. 3Icssrs.
ScJiimmcl t& Go. (Bericht, October, 1911, 110) distilled a certain
quantity of the sawdust and boards of the African wood, and
obtained the following results : —

Sawdust. Boards.

Yield of essential oil . . 3‘2 per cent. . . 3-24 per cent.

Specific gravity at ] 5° . . 0’9876 .. 1*0289

Refractive index . . . 1*50893 .. 1*61011

Optical rotation . . . —37° 10' • . . —32° 30'

133

PERFUMERY

Sawdust. Boards,

Acid value .... 14*9 . . 27*06

Ester value . . 8*4 . . 7*93

Ester value after acetylation . 70*0 . . 89*6

Solubility in 80 per cent, alcohol 1*6 vol. .. 2 vols.

Solubility in 90 per cent, alcohol 0*5 vol. . . 0*5 vol.

CEDRAT OIL. (See “ Citron Oil.”) — The cedrat oil of com-
merce is almost invariably a roixture of lemon with other Citrus
oils. The French “oil of cedrat ” is, when pure, citron oil, an
oil closely resembling lemon oil, having a specific gravity from
0*850 to 0*855 ; optical rotation, + 77° to -f 83° ; and refractive
index about 1*4750. It contains citral and terpenes. The French
“oil of citron ” is oil of lemon.

CEDRELA WOOD. — Cedi’ela wood must not be confused
with cedar wood, although its similar odour often causes it to be
so confused. Cedrela odorata is a native of the Caribbee Islands
and the Barbadoes. It grows to an immense size in Jamaica.
The wood has a pleasant cedar-hke odom’, hence it is often called
Jamaica or Hondm’as cedar. Cigar boxes are usually made from
tliis wood. It ^fields up to 1 per cent, of a fragrant essential oil
having a specific gravity 0*923 to 0*950, and refractive index
1*5040. Similar oils are obtained from the La Plata, Punta
Arenas, and Corinto cedar or cedrela trees. (S^ E. J. Parry,
“ The Chemistry of Essential Oils,” 4th ed., vol. i., p. 494.)

CELERY, OIL OF. — The seeds of the common celeiy,
Apmm graveoUns, jdeld about 3 per cent, of essential oil, which,
when distilled from the cultivated plant, is of considerable value
to the perfumer, both as a fixative and as an addition to floral
perfumes, such as sweet pea, etc. The oil has a specific gravity
0*860 to 0*895 ; optical rotation, -f 40° to -f- 82° ; and refraclive
index, 1*4780 to 1*4860. It owes its odour almost entirely to the
lactone sedanolide, Ci2lljg02. The oil has been critically examined
by Ciamician and Silber {Berichte, 1897, 30, 492, 1419).

CETACEUM. — Cetaceum or spermaceti is a sohd wax ob-
tained from the head of the sperm whale, Pliysctev 'niacrocsphalus ,
and other allied sea mammalia. It is deposited from the sperm
oil found in the head of these whales, and is purified by filtration,
re-melting and treatment with dilute alkali. It has the following
characters : specific gravity, 0*945 to 0*960 ; acid value, not
exceeding 1 ; saponification value, 125 to 138 ; iodine value, 3
to 5 ; melting point, 43° to 50° ; and refractive index about

134

PEBFU ME R Y

1-4330 at 80°. It consists principallj’’ of cetyl palmitate. Adultera-
tion -with stearic or other fatty acids is indicated h}’’ a Iiigh acid
value, and, if paraffin vax is present, the sample will not dissolve
clearh- in 50 to GO parts of boiling alcohol. Spermaceti is used to
a considerable extent in the preparation of creams and lip salves.

CHA HAVA. — Tins jdant, a species of GarncUia, is veiy similar
to the tea plant, hence its name of “ cha hwa,” or tea flower.
It is largely found in the wild state, flourishing on the slopes and
summits of the mountains in the jirovince of Che Kiang. The
chief utilit}'' of tea flower lies in its employment as a scent for
imparting aroma to the best quality of China tea. Often the
petals, as well as the entire flowers, are mixed with the tea to
increase its fragrance, and the resulting mixture, infused in the
picturesque Cliinese teacups, gives a particularly pleasant
beverage. Tliis plant also yields a nut, the size of an arachis nut,
having a brownish colour. These nuts, when subjected to ex-
pression, 3 'ield a liglit bro'^vn oil, which has a somewhat aromatic
odour. TJie oil is known locally as Cha Yon, or tea oil, and finds
extensive use in the coiffure of Chinese ladies. Its cultivation is
encouraged on this account, and it is especially valuable, being
easilj’ grown in situations suitable for little else.

CHAMP AGA FLOWER OIL. — ^This beautiful perfume has
no relationship with the so-called chamjjaca wood oil (q.v .) , It is
distilled from the flowers of Miclielia chainqiaca, probabl}'’ usuallj'’
mixed ■with the flowers of 3Iichclia loiiqifolia. The former yields
^mllow, and the latter wliite, flowers. The plants are natives of
India, and the oil is knowm to the natives as or chainpa-ka-
‘iiiter and other names. It is, in India , found principally in Nepaxil,
Assam, and Bengal. It is also cultivated in the Pliilippine Islands.
The perfume of the flowers is exquisite, but almost overpowering.
The native Indian women adorn their hair udth the flowers for
the sake of the perfume and for the rich yeUow-orange colom,
which contrasts so well with their black hair. The tree is highly
venerated by the Hindus, who have given one of its names,
Tulasi, to a sacred grove on the banks of the Yamxma. It is
also dedicated to the god Vislmu,

The follo^ving account is diie to Roiire-Berlrand Fils {Bulletin,
April, 1909, 24)

“ The tree is kno-wn by different names according to the
district : Cliampaca, Champaka in Bengal, Tita-sapa in Assam,
Oulia Gliamp. in Nepaul ; it is also known in other parts of the

136

PERFUMERY

country under the names of Sliav\2>ang, Shimbii, Sempangam,
Sampige, CliamgmJcam, Saga, Sapu, etc. This large tree, wliich is
an evergreen, prefers sandy soils. It is of fairlj’’ largo size, since a
man can scarceh'’ encircle the trunk vith his arms. This trunk
is gre}^ on the outside, and under the thiclc and greenish-coloured
bark the wood is nearly white. The branches present the same
external appearance. The leaves arc not veiy close together ;
thej" have long petioles, arc oblong in shajic, stiff, greenish brown,
brilliant above, paler underneath. The nerves are prominent on
the under -face.

“ The floAvers, of a 3'elloAv coloiu’, are produced at the tops of
the branches, and are carried by stout iAcduncles of a j-clloAAnsh
green coloiu’, polished and erect. The number of flower heads
ma}’ Amrj’ shghtl^" ; in general there are eight heads to the
verticillaster. The sepals are rounded at their extremities, the
petals are cuspidate. The stamens are numerous, the style is
short and stout. The fruits are on spilces or in bunches, round,
oblong, pale yellow when ripe. TIica* contain numerous seeds,
rounded on one face, flattened on the others owing to their
reciprocal pressure in the fruit.

“ There are two floAverings annuall}’, and the tree onh* A'iclds
fruits after some A'ears.

“ According to om- personal observations, the perfume of the
flowers of the Philippine chauipaca is stronger and sweeter than
that of the Singapore, Penang, Colombo and PeradeniA'a floAvers.
It Avould appear that it is the same AA'ith this tree as AAlth the jdang,
which does not Aueld the same essential oil in Java, the Straits or
Ce^don as in the Philippines. It is said that in India the seeds of
the chamj)aca are 3 *ellow’, whilst in the Philippines the}' arc cheny
red.

“ The A^ellow coloming matter of the floAvers is utilised in d3*eing.
The seeds 3'ield a fattj^ oil by pressing ; the flowers contain a
volatile oil, and 3deld, on distillation, a very pleasant aromatic
water. All parts of the plant possess a strongly spiced flavour.’’

Michclia champaca is generally cultivated, but is found AA'ild
over a large area. Cultivation greatly improves the perfume.
The oil has a specific gravit 3 ^ from 0-883 to 0-897, optical rotation
about — 13°, refractive index about 1-4470 at 30°, and ester
number about 180. It contains benzyl alcohol, linalol, geraniol,
esters of meth 3 d-ethyl acetic acid, meth 3 d anthranilate, iso-
eugenol, benzoic acid, meth 3 d-eugenol, and a cr 3 ^stalline bod 3 ' of
the formula CigHooC^, melting at 166°. Oil distilled in Manila

136

PERFV MERY

was found by Brooks {Philipp. Jour. Sc., 1911, 6, 333) to have a
specific gravity at 30730° between 0-904 and 0-9107 ; refractive
index, 1-4640 to 1-4688 ; and ester number, 124 to 146. An oil
distilled in the Malay Peninsula had a specific gravity 0-922 ;
optical rotation, + 12° 30' ; and ester number, 15-2. This oil
has little odour value. There are several other odorous species of
Michdia, but they are not used for distillation purposes. Cham-
paca odour is heavy and persistent, of the same type as ylang-
jdang and the larger varieties of perfumed lilies.

GHAMPAGA WOOD OIL.— See “ Bulnesia sarmienti.”

GHAMPAGOL. — ^This body is a crj’-stalline alcohol jjresent
in the oil of Bulnesia sarmienti (q.v.). It has been examined by
Wallach and Tuttle {Annalen, 1894, 279, 395). It has the formula
CigHggO, and was first named champacol by Merck, when it was
believed that the wood was true champaca wood, but has been
renamed guaiol. It is a crystalline body melting at 91°, apd boils
at 288°. It has a tea rose odour.

GHASSIS. — ^The name given to the wooden frames, usually
mth glass bottoms, upon which flowers are treated with fat
for the extraction of their perfume in the process known as
enfleurage {q.v.).

GHAVIBETOL. — This body, also known as betel-phenol, has
the formida C 10 H 12 O 2 . Chemically it is an. allyl-guaiacol, boifing
at 255°, of specific gravity 1-069 ; refractive index, 1-5413 ; and
optical rotation, + 8-5°.

GHAVIGOL. — ^This body, CgHujO, is a phenol occurring in bay
and betle oils. It is a highly odorous liquid, of specific gravity
1-035 ; refractive, index, 1-5441 ; optical rotation, 0° ; and
boiling point, 237°. Chemically it is para-oxyaUjdbenzene.

GHEIRANTHUS GHEIRI.— This plant is the wallflower, or
in France giroflee. It is a perennial plant of the natural order
Cruciferce, indigenous to southern Europe. The flowers jdeld a
mere trace of essential oil, so ‘that the natural perfume is not a
commercial article. Kummert {Ghem. Zeit., 1911, 667) has made
an exhaustive examination of the oil obtained, to the extent of
0-06 per cent., by extracting the flowers with a volatile solvent
and distilling the oil. He found it to have a specific gravity 1-001,
and a saponification value 20-35. He found present nerol, geraniol,
linalol, benzyl alcohol, indol, methyl anthranilate, esters of
salicylic acid, a para-cresol compound, a lactone, and probably
irone and anisaldehyde. An artificial perfume named cheiranthin

137

PERFU ME Rl

is compounded on the basis of the above details, and probably
also contains isoeugenol and isobutyl-phenyl acetate. Hydroxy-
citronellal and jpam-cresol methyl ether are also employed,
especial!}^ the latter.

CHEVREFEUILLE. — A name for honeysuclde perfume {q.v.).

GHLOROSTYROL. — Styrolene (phenyl-ethylene), CgHg,
jdelds two sets of halogen derivatives, of which the a
derivatives are useless in perfumery, but the cu derivatives have a
powerful hyacinth odour. co-Chlorostyrolene, CgHgCH : CHCl, is
obtained by the action of caustic allcali on dichlor-ethyl benzene.
Its odour, however, is not so fine as co-bromostyrolol {vide
“ Bromostyrol ”). It boils at 198° to 199°.

CHRYSANTHEMUM OILS. — Clirysantliemxihn marginatum
(natural order Composiice) is a plant indigenous to Japan, where
it is known as Isolciku. According to Shinosaki {Jour. Gliem. hid.
Tokyo, 1919, 22, 455) it jdelds O’ 005 per cent, of essential oil, of
a gi’eenish blue colour, having the following characters : —

Specific gravity ..... 0-9231

Optical rotation . . . . . — 47°

Refractive index ..... 1’5020

Saponification value . . . .16-3

Saponification value after acetylation . 63

The oil is aromatic, but its constituents have not definitely been
identified. This oil may be identical with that described by
Perrier {Bull. Soc. Chim., 1900, iii., 23, 216) under the name kiku
oil, from Clirysaniliemum J aponicum, although the characters of
the two oils are different. The flowers of Chrysanthemum cineraria-
folnim, which provide the insect powders of commerce, jdeld an
essential oil with a poAverful odour. Its constituents have not
been completely investigated (Siedler, Berichie Deutsch. Pharm.
Ges., 1915, 25, 297).

CHYPRE. — This name is a fancy one, which has become of
very common application in the perfume industry. It is a perfume
of heav}^ odour, which is usually based on musk, verbena and
sandalwood with a little sassafras oil or safrol, with mousse dc
chCnc or benzoin as a fixative. Clary sage oil is also frequently
present, and often a little bergamot oil.

CINEOL. — See “ Eucaljqptol.”

CINNAMIC ACID.— Cinnamic acid, CgHg.CH : CH.COOH,
is found, both in the free state and in the form of esters, in various

138

PERFU HER Y

essential oils, especially those of balsamic substances such as
storax. It is a crystalline body, melting at 133°, and boiling at
300°. It lias a pleasant odour and is useful as a fixative, as tbe
odour is not too pronounced. It is prepared artificially by beating
2 parts of benzaldehyde and 3 parts of acetic anhydride Avith
1 part of fused spdium acetate, to 180° for twelve hours. The
reaction mass is extracted with water, and the cinnamic acid
precipitated from the aqueous solution b}’- hydrochloric acid. It
is also prepared on an industrial scale by heating benzyhdene
chloride with fused sodium acetate to 200°.

Claisen {Berichte, 1890, 978) prepares it bj’' treating ethyl
acetate and sodium with benzoic aldehyde at ice temperature.
(See also the various cinnamyl esters.)

Synthetic cinnamic acid is a mixture of two isomeric acids.
It is composed of an acid identical vdth the natural acid
(a-cinnamic acid) and a-heterocinnamic acid.

a-Heterocinnamic acid ma 3 >‘ exist in two forms. In a recent
paper {Berichte, 42, 2649, 2655), Erlenmeyer has undertaken a
study of the conditions of formation of these various isomerides
in nature, and also of the S 5 mthetic cinnamic acids, prepared
according to the different known methods. These modes of
formation, which are very numerous, are summarised in a table
attached to the paper, to which the reader is referred.

Erlenmeyer first shows that heterocinnamic acid exists, although
in very small proportions, in the natural cinnamic acid extracted
from stj'rax benzoin.

It appears to follow, from a critical examination of the synthetic
methods which make use of benzaldehyde as their startmg point,
that, to a large extent, the variations observed in the properties
of the cinnamic acids obtained shordd be attributed to the influence
.of impurities in the raw material.

Thus, natural benzaldehyde, which alw.ays contams a certam
quantity of hydrocyanic acid, and which gives rise mainly to
a-cinnamic acid when treated according to Perkin’s method,
behaves, after all the hydrocyanic acid has been eliminated, like
the synthetic aldehyde, which yields, under the same treatment,
storacic acid and the a and modifications of heterocinnamic acid.
-(See also Campbell and Sudborough, Jour. Ghem. Soc., 95, 1538 ;
Liebermann and Trucksass, Berichte, 42, 4659, 43, 411 ; and
Riber and^Goldschmidt, Berichte, 43, 453.)

CINNAMIC ALCOHOL. — ^This substance, of the formula
CcHg.CH : CH.CH 2 OH, is also known as styrone. It exists,

139

PERFUMERY

principall}' in the form of its acetic and cinnamic esters, in storax,
balsam of Peru, and in hyacinth and other floral oils. Much of
the commercial substance is prepared by the hydrolysis of the
cmnamic esters present in storax. It is prepared' artificially by
reducing cinnamic aldehyde diacetate by means of iron and
acetic acid, and saponifjdng the resulting esters. It is a crystalline
bodj^, melting at 30'* to 33°, but commercial specimens almost
invariably contain traces of impurities which keep it in a liquid
condition. It has a specific gravity about 1*020 (commercial
specimens vary from 1*015 to 1*030) ; refractive index, 1*5720 at
30° ; and boiling point, 258°. The odom- of cinnamic alcohol is
weak, but very sweet and delicate. It is useful in the preparation
of artificial h 3 ’-acmth and snnilar floral odours,

CINNAMIC ALDEHYDE. — ^This aldehj’de is the principal
odorous constituent of cinnamon and cassia oils. Its formula is
CcHg.CH : CH.CHO. It can be extracted from the oils in which
it occurs by shaking it with a hot solution of sodium bisulpliite,
which combines with the aldehj^de to form a soluble compound.
The aqueous solution is separated from the non-aldehj’-dic con-
stituents, which float on the surface of the liquid as an .oil, and
on the addition of dilute sulphuric acid the aldehyde is liberated
from the bisulphite compound, and can be distilled in a current of
steam.

Cimiamic aldehj^de is prepared on a comparatively large scale
by condensing benzaldehj’-de vdth acetic aldehj^de in the jpresence
of an alkali. This method, originaUj'- due to Boehringer (German
Patent 19018), is as follows : A solution of 5 parts of benzaldehyde
and 5 parts of acetic aldelij’-de in 10 parts of alcohol is cooled to
10°, and 10 parts of a 25 per cent, solution of caustic soda solution
in water are gradual^ added, the addition taking from five to ten
minutes. The temperature should not be allowed to rise. When
the liquid is cpiite transparent, it is allowed to stand for twent}*-
minutes, and is then poured into an excess of water. The separated
cinnamic aldehj^de is purified by rectification. For perfumery
purposes cinnamic aldehj^de should be free from chlorine.

Pure cinnamic aldehyde should have a specific gravit}'- from
1*054 to 1*057 ; optical rotation, 0° ; refractive index, 1*6195 ;
and boiling point, 253°.

It is employed to a considerable extent where a powerful
ciimamon odour is required without the delicacy of the natural
product. It is also used in the preparation of an artificial oil of
cinnamon. {Vide “ Cinnamon.”)

140

PERF UMEB Y

CINNAMOMUM CEGIODAPHNE.— See “Nepal Sassa-
fras.”

CINNAMOMUM GLANDULIFERUM. — See “ Nepal
Sassafras.”

CINNAMON, — ^Tlie odour of cinnamon has from time
immemorial been highly appreciated by the perfumer. The
principal products of odour value are : the essential oil distilled from
the bark, ■wdiich is the ciimamon oil, properly so called, of com-
merce ; and the essential oil distilled from the leaves, valued as a
soiu’ce of eugenol. A good deal of the oil of cinnamon distilled in
Ceylon is, in fact, a mixture of bark and leaf oil.

The plant yielding these products is Ginnamoniwn zeylanicum,
a native of Cejdon, found in moist low country up to an elevation
of about 2,000 feet. The tree is also grown in India, Mauritius,
the Seychelles, and Jamaica, but the greater part of the world’s
supply is derived from Ceylon. It has been stated to occur wild
^ in the Malay Peninsula, but according to H. N. Ridley, the
Director of the Botanic Gardens, Straits Settlements, this is
doubtful. He has found the allied tree Cinnamomum inero there,
and whilst it is almost impossible to detect any botanical differ-
ences between tins tree and the Ceylon cinnamon, the taste and
odour of the barks are quite different. He considers it probable
that the true Ceylon cinnamon is a very aromatic form of C. inero.
It is probable that the cinnamon mentioned in early writings
was in fact cassia, which was certainly imported into Arabia
from China in very early days.

In the sixteenth century Ceylon cinnamon was entirely derived
from wild trees, and the collection of the bark was controlled by
the Portuguese, who had occupied the island in 1536. About
100 years later the Dutch took the island, and in 1770 De Koke
commenced the cultivation of the tree, and the Dutch obtained
about 200 tons of bark annually, burning the bark when supplies
were excessive in order to keep the price up.

"The “ cinnamon gardens ” of Ceylon are situated principally
in the south-west of the island. The bark is exported either in
the form of pipes or quills, or in the form of chips or small frag-
ments, the latter being used for the distillation of the essential
oil. The oil distilled in Ceylon is usually obtained by macerating
the chips in brine for a few days and then subjecting them to
distillation. The yield varies from 0-5 to 1 per cent. A con-
siderable amount of the bark is distilled with the addition of

141

PEB.FU MER 7

leaves, or cinnamon leaf oil is added to tlie oil distilled from tlie
bark. In purchasing Ceylon distilled oil it is necessary to examine
the product from this point of view, as the leaf oil has none of the
characteristic cinnamon odom’, but closely resembles clove oil.

The oil of ciimamon bark owes its odour to its principal con-
stituent, cinnamic aldehyde {q.v.), but, of course, modified by the
presence of secondar}’- constituents. The characters of the oil
depend on the condition of the raw material, and also on the
method of distillation employed. The oil distilled on the Continent
generally possesses a higher specific gravity than that distilled
in England, and that distilled in the Seychelles differs very
considerably from all other bark oils. The following figures are
given by E. J. Parry (” Chemistrjr of Essential Oils,” 4th ed.,*
vol. i.) : —

English distilled. 1

Continental dis-
tilled.

Seychelles oils.

Specific grawty .

0-995-1-040

1-020-1-040

0-943-0-975

Optical rotation .

0° to — 1°

1 — l°to— 3°

Eefractive index .

1-5700-1-5850

1-5850-1-5910

1 1-5280-1-5335

Cinnamic aldehyde

58-70 per cent.

63-76 per cent.

25-36 percent.

Ce 3 don cinnamon bark oil contains, in addition to cinnamic
aldehj^de, the following bodies : methjd-amyl ketone, pinene,
phellandrene, cymene, benzaldeh 5 ’-de, nonylic aldehj^de, eumic
aldehyde, linalol, finalyl isobutyrate, eugenol, and caryoplij^Uene.

Cinnamom leaf oil is entirely different from the bark oil. It
consists mamly of eugenol (up to 95 per cent.), which can be
extracted and used for the manufacture of vanillin. This oil has
a specific gravity from 1-040 to 1-065 ; optical rotation, — 0° 10'
to -|- 2° 35' ; refractive index, 1-5300 to 1-5450 ; and eugenol
value, 70 to 95 per cent.

It has been stated that Madagascar cinnamon leaf oil contains
a considerable amount of benzyl benzoate. This requires con-
firmation, but the eugenol in this oil should be determined in
the cold, as otherwise benzyl benzoate is decomposed and inter-
feres with the accuracj- of the determination.

Samples of cinnamon bark oil from the Gold Coast have been
examined at the Imperial Institute. Three samples' were reported
upon in the Bull. Imp. Inst., 1919, V7, 189, and compared with a
sample previously reported upon {ibid., 1918, 16, 146).

142

PERFU 31EB 1

The three samples were as follows : —

No. 1. From Assiiant^i . — ^This eonsisted of pieces of rolled
hark, of pale reddish bro-rni colour, about 10 inches in length and
1 inch in uddth. The roUs were very irregidar in shape, and much
scarred and tom.

The aroma of tliis material was inferior to that of Ceylon
cinnamon bark.

No. 2. From Cooma-ssie . — ^This sample consisted of rolls of bark
measming 12 inches in length and 1 to 1^- inches in width. The
material resembled sample No. 1, but possessed a better aroma.

No. 3. From Ahuri . — ^This bark v'as in rolls about 91 inches long
and f inch wide. It was similar in appearance to sample No. 1,
though somewhat paler, wliilst the aroma was more fragrant than
that of sample No. 1, but not equal to that of sample No. 2.

Distillation trials were carried out with the tliree barks at the
Imperial Institute in order to deterniine the yields of volatile oil
which they furnished, and the results are shown below in com-
parison with the corresponding figures for the previous sample
from Tarquah referred to above : —

Saraplo
No. 1
from

Assuantsi.

Sample
No. 2
from

Cooma^sio.

Sample
No. 3
fro m i
Aburi,

Sample
No. 4
from
Tarquah.

“ Heavj’’ ” oil which sepa-
rated from the aqueous

Por cent.

Per cent.

distUlate

“Light” oil extracted with
ether from the aqueous

1-5

1-6

1-4

it3

distillate ....

0-4

0 3

0 30

Total yield of oil

1-8

1-7

1 48

It will be seen that the jdelds of oil from the later samples are
somewhat higher than that fui-nished hj the original sample from
Tarquah. They are also considerably in excess of those yielded
by Ceylon cinnamon bark, which vary from 0-5 to 1 per cent.
The samples had the following characters : —

1 .

Specific gravity

1-038

1-042

1-041

1-042

Refractive index

1-5940

1-G050

1-6030

Aldeliydes

74 per cent.

88 per cent.

86 per cent.

143

PE.RFU MEB7

Roiire-Berlrcnid Fils [Bulletin, October, 1920, 36) have examined
a cimiamon oil from Amiam, wliicli had the following characters : —

Specific gravity ..... 1-051

Refractive index at 17° . . . 1-6090

Optical ]’otation . . . . . — 0° 8'

Acid value . . . . .2-8

Aldehydes 95 per cent.

The root bark yields an essential oil, but it is not an article of
commerce.

A Japanese plant, Cinnamomum Lozireirii, jdelds an essential
oil which contains about 25 to 30 per cent, of cinnamic aldehyde.

Cinnamomum glan chili ferum (or G. Cecioclaplme ?), the Nepal
sassafras tree, is highly odorous, and its leaves jfield an essential
oil, which, however, contains httle, if any, cinnamic aldehyde.

Culilavan oil is the product of the bark of Cinnamomum
Culelaicau. It contains about 60 per cent, of eugcnol and some-
what resembles ordinaiy cinnamon leaf oil.

The so-callcd Brisbane “ white sassafras ” is Cinnamomum
Oliveri. Its bark vfields an essential oil containing phenols, but no
cinnamic aldehyde.

The exports of cinnamon bark (apart from oil) from Ceylon
amount to between 2,000,000 and 3,000,000 lb. per annum.

For details of the cultivation of cinnamon, its diseases, and the
preparation of the bark for export, see “ Spices,” by H. N. Ridley
(Macmillan & Co., Ltd., London).

CINNAMEINE. — ^This name is used loosely to signify the
mixture of benzyl benzoate and cinnamate present in balsam of
Peru, etc. Strictly, it is sjmoiymous vith benzyl cinnamate [q.v.).

CINNAMYL ACETATE.— This ester has a sweet floral
odour. It has a specific gravity 1-0184, refractive index 1-5295,
and boils at 262°.

CINNAMYL BUTYRATE. — ^This ester, of the formula
CcHg.CH : CH.CH2.C02(C3H7), has a fine fruity odour. It must be
used in very small quantities. It is prepared bj’- the esterification
of cinnamic alcohol and but^rric acid. It has a specific gravity
1-023, and refractive index 1-5255.

CINNAMYL CINNAMATE. — ^This ester, knovm also as
st3T:acin, occurs naturally in storax and other balsamic substances,
and probabty, in traces, in essential oil of hyacinth. It is also
prepared artificially b^’' the esterification of the alcohol and the
acid. It forms a crystalline mass melting at 44°. It has a sweet

144

PERFU MEB Y

heavy odour resembling that of balsam of Peru. Its formula is

• CH.CHo-COj.CH : CII.CgH 5 . Its specific gravity is
1-040 at 25°.

^ GINNAMYL PROPIONATE. — ^Tho odour of this ester,

• GII.CH 2 .C 02 (C 2 Hg), resembles that of grapes j it is
used in the manufacture of fruit and floral odours.

CISTUS CRETIGUS. — See “ Labdanum.”

GITRAL.— Citral, or geranaldohyde, CioHigO, is an aldehyde,
or, more properl}’', a mixture of t'wo isomeric aldeh 5 ’'des, and is
the characteristic odour bearer of lemon oil, lemongrass oil, true
verbena oil, and the oil of Baclchoiima citriodora, in each case
modified by the presence of subsidiary constituents. Citral as a
commercial article is practically entirely extracted from lemon-
giass oil, as, on account of price, the oil of Backliousia is unable
to compete. It occurs in numerous essential oils, and may be
obtained by the oxidation of geraniol, nerol, and linalol. Com-
mercially it is extracted from lemongrass oil, previously fraction-
ated, in the form of its bisulphite compound, from which, after
pressing and draining, it is removed by decomposition with a
dilute acid and distillation with steam. Thus, prepared com-
mercial citral is a pale yellow oil with an intense lemongrass odom*
— so powerful that, after smelling it, the nose is frequently
paralysed and unable to smell anytliing else for some hours. It
is a mixture of a-citral or geranial and /3 -citral or neral. The
commercial mixture and the two isomers have the foUo'wino'
characters : — °

“Citral.”

a -Citral.

/3-Citral.

Specific gravity at 20°

0-890-0-893

0-890

0-889

Refractive index .

1-488-1*490

1-4891

1-4890

Boiling point at 20 mm. .

119°

118°

The principal importance of citral to the perfumer is the fact
that it is the sole raw material from winch ionone and similar
artificial violet perfume materials can be manufactured. As such,
citral is only used to a small extent in perfumes, but in certain
cases it imparts as harp odour to floral bouquets which is much
appreciated. (For the conversion of citral into 'ionone, vide
“ Ionone.” For the determination of citral, see “ Aldehydes,
Determination of,” and “ Lemon, Oil of.”)

145

, PE'RFUMEBY

GITRAPTENE. — ^Tliis substance is the main constituent of
the non-volatile residue of lemon oil. Its formula is CuHioO^,
and its melting point 146° to 147°. It is a dimethoxy-coumarin.

CITRON OIL.— See “ Cedrat Od.”

^ GITRONELLA OILS. — There are two main tj^pes of these
oils, namelj’", “ Ceylon ” and “ Java.” Oil of the former tj’pe is
produced chiefly in Ceylon, while oil of the latter tj'pe is produced
in Java, Federated Malay States, and Burma.

The Ceylon type is distilled from the grass Cywhopogon Nardus,
Rendle (Lenabatu grass) {Bull. Imp. Inst., 9 , 1911, 240, 333 ),
while the Java type is distilled from the grass Cynihopogon
Winisrianus (Maha Pengiri grass) {K&w Bulletin, 1906, 8 , 297).'
Both types of oil are chiefly used for perfumery purposes, and
mainly in the soap industry.

Ceylon Citronella Oil.— This t 3 rpe is almost entirely distilled
from grass cultivated in south Ceylon, although small quantities
are also produced in the Seychelles and the island of Mayotte.

The exports of this oil from Ceylon for the 5 'ear 1922 were
1,325,355 lb., and for 1923 they amounted to 1,118,619 lb. Of
these the United Kingdom took 313,403 lb. in 1922, and 379,200 lb.
in 1923 ; while the United States took 779,951 lb. in 1922, and
571,841 lb. in 1923 {SchimmeVs Bericlit, 1924, p. 14).

The oil is distilled by natives in qmte primitive stills, which
produce about 25 lb. of oil per day, the yield of oil being 0*5 to
1 per cent, of the grass.

Practically all the Ceylon citronella oil that is dealt in com-
mercially is adulterated with a small quantity of kerosene,
although a pure grade is obtainable under the description of
“ estate oil.”

In order to restrict the amount of adulteration, a test was
dev sed by Messrs. Scliimmel, and this test has long been known
as ‘ Schimmel’s test,” and is sometimes incorporated in com-
mercial contracts, wliich set out that the oil sold is “ guaranteed
to pass Schiramel’s test.”

This is purely a solubiHty test, and depends on the relative
insolubility of kerosene in 80 per cent, alcohol. It was soon
found, however, that it was not capable of detecting the presence
of less than 5 per cent, of kerosene, and I\Iessrs. Scliimmel, there-
fore,^ mtroduced a further test, which they caled the ‘‘raised
test, but it has not come into general use in England or the
United States.

146

PERFUMERY

Messrs. Scliimmers iastructions (SchimmeVs Bericht, 1923, p. 18)
for caiTjang out these tests are as follows : —

Schimmd's Test . — Citronella Oil shall be soluble to a clear
solution in 1 or 2 volumes of 80 per cent, alcohol (specific gravity,
0-8642 at 15° C.). This solution, on addition of further volumes
of 80 per cent, alcohol, shall become not more than slightly
opalescent and show no marked turbidity. The alcohol shall be
added gradually, and if a turbiditj’^ does develop, further alcohol
is added until the turbidity reaches a maximum. When the
maximum turbidity is obtained, the solution is carefully examined
to see whether any oil3’' droplets have separated out. If no
separation of oily droplets is shown, the oil is said “ to pass
Schimmel’s test.”

In no case must more than 10 volumes of alcohol be
used, and the oil and alcohol mixture should not be violently
shaken, as otherwise the oilj'' droplets may become too finely
divided.

In England (P. dk. E. 0. R., June, 1923, p. 179, vol. xiv.. No. 6)
tliis test is often carried out in a slightlj’’ different manner ;
instead of the 80 per cent, alcohol being added gradually, 10
volumes of 80 per cent, alcohol are added to 1 volume of Cejdon
citronella oil ; tliis mixture is shaken and allowed to stand for
tw-enty-four hours, after which time no oily droplets should have
separated.

Schmimel’s Raised Test . — ^To the original oil 5 per cent, by
volume of petroleum is added, and this mixture is then tested by
the ordinary Schimmel’s test.

Both these tests are purely empirical, and, while easj’’ and
convenient to carry out, are by no means conclusive proof as to
the purity of the oil or the extent of the adulteration.

In 1923 large quantities of citronella oil were shipped to America
and England which “ passed Schimmel’s test,” but these oils were
even more heavily adulterated vdth kerosene than usual ; in
order, however,’ to cover the adulteration, alcohol had been added
to the oils so that they should pass Scliimmel’s test, and in some
cases the amount of alcohol that had been added amounted to
20 per cent.

When these oils were washed with three times their volume of
1 per cent, sulphuric acid, which removed the alcohol, the washed
oils no longer passed Schimmel’s test, and both the specific gravity
and refractive index of the washed oils were materially higher
than those of the unwashed oils.

147

10 -a

PEBFU MERY

A pui’e Ce3don citroiiella oil known commercially as “ estate
citronella oil ” has the following characters : —

Specific gravity at 15-5° C.
Oj)tical rotation

Refractive index at 20° G. .
Acetyli sable contents (as geraniol)
Solubility in 80 per cent, alcohol .

0-900-0-920

— 7° to — 18° (usually
about — 12°).

1.480-1*490.

GO per cent.-G3 per cent.

1 in H volume, and
passes both Schimmel’s
Test and Schimmel’s
Raised Test.

On distillation, no fraction should distil below 1G0°C. (absence
of alcohol and light pcti’oleum).

The first 10 per cent, distilled under reduced pressure (20 to
40 mm.) must have a specific gra%uty not below 0*858, and a
refractive index at 20° C. not below 1*457 (Parry’s “ Chemistry of
Essential Oils,” 4th ed., vol. i., p. GG).

When washed with three times its volume of 1 per cent, sulphuric
acid, the refractive index of the washed oil should not show an
increase of more than 0*0005 at 20° C. (absence of alcohol).

The characters of tlie usual commercial quality of Ceylon
citronella oil, and which oil is sold under the description “ Cejdon
citronella oil passing Schimmers test,” are as follows : —

Specific gravity at 15*5° C. .

Optical rotation

Refractive mdex at 20 ° C. .

Acetyhsable contents (as geraniol)
Solubihty in 80 per cent, alcohol .

0*895-0*910 (usually not
less than 0*900).

— 7° to — 18° (usually
about — 12°).

1*479-1*485 (usuall}’’ not
less than 1*4815).

55 per cent.-5S per cent.

1 in l^- volume, and
passes Schimmel’s test.

When washed with three times its volume of 1 per cent, sulphuric
acid, the refractive index of the washed oil should not show an
increase of more than 0*0005 at 20° C.

This oil is distinguished from pure Cejdon citronella oil by — ^

(1) Its lower content of acetyhsable constituents.

(2) It usuaU}’- does not pass Schimmel’s raised test. -

(3) The lower specific gravity and refractive index of the first
10 per cent, distilled under reduced pressure (Parry’s “ Chemistry
of Essential Oils,” 4th. ed., vol. i., pp. G5-GG).

Parry and Bennett have fractionated samples of genuine Ceylon
citronella oil, samples adulterated with definite amounts of

148

PEBFU MEJR I

petroleum and resin spirits, and samples of the usual market
quality of Ceylon eitronella oils, and find the characters of the
first 10 per cent, distilled from the oil to be as follows : —

Pure CifroncUa Oils

Specific cravitv at

15 >C. *

Rotation in 100 mm.
tube.

Refractive index at
19° C.

O-SGl

— 44°

1-4G80

0-SGl

- 43°

1-4732

O-SGO ;

- 35°

1-4G92

0-SG3 !

- 23°

1-4G55

-0-SGG j

— G°

1-4590

0-SC7

- 11°

1-4571

Gilroneila Oils mixed with AduKeranis

Specific
gravity at
IG-r/C.

Rotation
in 100 mm.
tube.

Refractive
index at

10° G.

1 E + 5

iier cent, resin spirit

0-855

1-4563

2 E + 10

0-848

l*4o45

3 E + 15

/J 31 !

0-841

1-4525

4 E d- 20

33 33 i

0-833

1-4505

5 D -f 5

M 33

0-854

- 17°

1-4.570

6 D -f 10

33 33

0-845

- 14°

1-4515

7 D + 20

33 33

0-835

1-4490

8 C + 10

per cent, iictroleum
spirit ,

0-848

1-4514

Adidieraicd Citronella Oils on the Market

Specific gravitj” at
15-5° C.

Rotation in 100 mm,
tube.

Refractive index at
19° C.

0-822

— 26° 48'

1-4492

— 23° 50'

1-4504

— 18° 20'

1-4525

— 22°

1-4486

1-4540

0-836

— 29°

1-4495

149

PERFU MERY

Resin and Pcirolenm Spirits

! ^Specific
giavily at

j Potation

1 in lOO nnn,
i tube.

Pofractivc
index at

10° C.

1, Eesin spirit .

O'SOG

+ 4°

1-4403

9 '

0-802

+ 2° 30'

1-4425

3. Petroleum spirit (tur- i
pentinc substitute) . '

0-798

+ 1°

1-4435

4. 1

0-801

+ 1° 30'

1-4416

Tlie lightest fraction wliicli Parrj’’ and Bennett obtained from the
adulterated oils had a specific gravity of 0-79S, an ojjtical rotation of
— 17°, and commenced to distil at 112° C. In none of the fractions
was any pronounced odour observed, nor any fluorescence ; hence
the conclusion that resin spirit is the adulterant.

The acctylisable constituents of Ceylon citroncUa oil consist
in the main of a mixture of geraniol and citronellal. in which the
geraniol predominates, although small amounts of acctylisable
compounds, such as borncol, etc,, have also been identified.

Regarduig the proportion of geraniol to citronellal, Messrs,
(Schimmel {SclihnmcVs Rej^orl, April, 1923, 44, and April, 1914,

p. 44) have examined five samjilcs of Ce 3 don citroncllo oil, with the
following results : —

Specific

gravity.

[

1 Rotation.

Total

acotyli&ablo

constituents.

Gcran'ol.

Plitlialic

anhydride.

j Citronellal.

' Klobcr’s
j Jlothod,

1 Piicn}'!-
1 liydrazino.

Dupont’s

method.

Oxime.

Per rent.

Per cent.

Por cent.

0-9012

— 11° 22'

54.1

30-7

11-4

7-9

0-9016

— 11° 28'

57-2

33-2

11-0

8-0

0-9034

— 11° 40'

58-6

30-0

11-6

7-8

0-9039

— 11° 43'

56-3

29-8

10-8

6-7

0-9033

— 11° 31'

57-6

30-8

11-5

7-9

From these and the values previously obtained, Messrs.
Schimmel set out the following limits : —

Per cent.

Geraniol ..... 29-6-34-4

Citronellal (Kleber) . . . 7* 5-1 1-6

Citronellal (Dupont) . . .6-6- S'O

160

PERFU MEB Y

A critical examination of the chemical constituents of a pure
sample of Ceylon citronclla oil carried out by Messrs. Schimmel
{SchimmeVs Rcporl, April, 1912, p. 44) resulted in tlio presence of
the following compounds being identified ; citronellal, camphene,
dipentene, borncol, gcraniol, methyl-heptenone, methyl-eugenoli
esters of valeric acid, a tcrpene of very low specific gravity, a
body related to linalol, thujono, ncrol, d-citronellol in the
form of acetic and but\Tic esters, gcranyl acetate, and a high
boiling Irevorotatory h.ydrocarbon C 13 H 0 ,.

Ja^-a Citronella Oil.— This oil is chiefly produced in Java,
although an increasing amount is now also produced in Burma
and the Federated Malay States (“ JIalay Citronclla Oil ” P <£?
E. 0. R., vol. XV., No. 4, p. 120).

For the 3 'car 1921 Java e.xported {SchiinincVs Ecricht, 1924,
p. 17) 273,140 kg., but in 1922 this rose to 434,708 kg.

Of these quantities, 13,052 kg. and 137,944 kg. were exported
to England for 1921 and 1922 respectively, while to the United
States the exports amounted to 100,931 kg. for 1921 and
97,900 kg. for 1922.

In Java {SchimmeVs BericM, 1924, p. 17) the oU is distilled
from the fresh grass, the grass being cut after the first six months,
and then every four months for a period of four years, after which
the plants must be replaced. There are approximate!}'- 15,000
acres in cultivation, and the 3 neld of oil is 50 to GO lb. per acre

per 3 'ear, and there are thirty-five factories employed in distilling
the grass. °

The characters of the oil produced in Java and Malay are practi-
call}' identical, but those of Bunnese oil are somewhat different.

All these oils differ materially from that of the Ceylon t 3 'pe,
not only in odour, but also in physical and chemical charactei’s,
their main difference being much higher contents of citronellal
and total acet 3 disable contents.

These oils are sold on the basis of their acet 3 disable con-
stituents, those from Java and Malay being usually bought on a
basis of not less than 85 per cent. acot 3 'lisable constituents
calculated as gcraniol, while for the Burmese oil an acetylisable
content of 90 per cent, is often stipulated.

These oils are not often adulterated, and rarely suffer the gross
adulteration that is common to Ce 3 don citronella, although at
intervals they suffer adulteration with fatty oils {P. & E. 0 R
July, 1923, vol. xiv.. No. 7, p. 254), and Messrs. Schimmel have
examined two samples adulterated with motor spirit.

161

PE BFV MEET

The characters of the oil produced in Java and the Federated
Malay States are as follows : —

Specific gravity at 15-5° 0.
Optical rotation

Eefractive index at 20° C.

Acet 3 disahle contents (as geraniol)

Non-volatile residue at 100° C. ^
Solubility in 80 per cent, alcohol ^

0- 885-0-895

0° to —3° (rarely
slightly +).

1- 460-1-472 (seldom

less than 1*468).

80 per cent, to 92 per
cent, (usually not
less than 85 per cent.)

1*5 per cent, to 5 per
cent.

1 in 2 volumes, and Ire-
coming not more
than slightly opales-
cent in 10 volumes.

When washed with three times its volume of 1 per cent, sulphuric
acid, the refractive index of the washed oil should not show an
increase of more than 0*0005 at 20 C. (absence of alcohol), and
as a rule the refractive index of the washed oil is slightly lower
(up to 0*001) than that of the original oil.

Not more than 24- per cent, should distil below 208° C.

The acetjdisable constituents of Java citronella oil consist, in
the main, of a mixture of geraniol and citronellal, in which the
citroneUal predominates.

Messrs. Scliimmel {ScJiimmeVs Ee^Jort, April, 1913, p. 44, and
April, 1914, p. 44) have examined seven samples with special
reference to their geraniol and citronellal contents, and give the

folloving figures : —

Specific

gravity.

1 Rotation.

Total

acetyli^able

contents.

Geraniol.

1 Citronellal.

Klebor’s

motbod.

Dupont’s

method.

Per cent-

Per cent. 1

Per cent.

0*8913

— 2° 15'

85*4

35*3

36*0

36*6

0*8859

- 1° 45'

87*6

35*3

- 40*0

45*2

0*8866

— 1° 35'

88*7

36*4

-40*0

46*3

0*8868

— 1° 22'

88*0

33*5

38*8

39*5

0*8883

— 1° 28'

87*5

40*1

38*7

35*4

0*8925

— 2° 11'

84*7

35*9

38*0

37*2

0*8881

— 1° 11'

91*0

37*0

36*8

40*1

1 P. tk E. 0. B., July, 1923, p. 254, vol. xiv.. No. 7.
162

PEUFU MERY

From these and previous results they suggest the following
limits : —

Per cent.

Geraniol . . . . . 26-G 40-1

, Citroncllal (Kleher) . . . 35-41

Citroncllal (Dupont) . . . 35-4G

Oils produced in Burma usually have the following characters : —

Specific gravity at 15'5° C. . . 0'890-0-n00.

Optical rotation . , . . 0 to 2° (very rarel^f

slightlj’ — ).

Eefractivc index at 20° C. . . l*4G9-l-472.

Acetj'lisable contents (as geraniol) 89 per cent, to 93 per

cent.

Non-volatile residue at 100° C. ^ .2 per cent, to 5 per

cent.

Solubility in 80 per cent, alcohol ^ . 1 in 2 volumes, becom-

ing not more than
opalescent in 10 vols.

As in Java citronclla oil, the acetylisable constituents of Burma
citronella oil consist in the main of a mixture of geraniol and
citroncllal, but the amount of geraniol iwcsent is.usuallj’’ somewhat
higher than that found in Java citronclla oil, and often amounts
to 50 per cent, of the oil,

Burma citronella oil is, as a rule, distinguished from that
produced in Java by —

(a) The optical rotation of the Burma oil is usuall}’’ to the right,
wliile tliat of the Java is almost invariabl}’^ to the left.

(&) The refractive index and specific gravity of the Burma
oil are relatively higher for the same total acet 3 disable contents
than those of the Java oU.

In the case of Burma citronella oil a specific gravity of 0-893
would indicate an acetylisable content of about 92 per cent.,
wliile for an acetylisable content of 90 per cent, the specific
gravity would be about 0-89G. In Java oil a specific gravity of
0-893 is usually found, together vith an acetylisable content of
about 8G per cent., while for an acetylisable content of 90 jier
cent, the specific gravity would be about 0-888.

Fm'ther references to citronella oil : —

“ Separation and Detection of Benzine and Petroleum ” (Dodge,
Eighth International Congress of Applied Chemistry, 1912, vol. vi.,
p. 8G).

1 P. & E. 0. It., July, 1923, p. 264, vol. xiv.. No. 7.

163

PERFU HER Y

'‘Anatysis of Oil of Citronolla ” (P. dh E. 0. R., June, 1913,
voL iv., No. C), p. 107).

Effect of Climate on Burma Citronella Oil ” (P. c& E. 0. R.,
Tol. T., No. 12, p. 398).

“ Some Abnormal Samples of Java Citronella Oil ” (P. <b
E. 0. R., vol. V., No. 8, p. 275).

“ Formosan Citronella Oil ” (P. cb E. 0. R., vol. yii., No. 9,
p. 279 ; vol. ix., No. 13, p. 323 ; vol. x., No. 10, p. 240).

“ Specific Gravity of Ceylon Citronolla Oil at Temperatui’cs
from 15° to 35° C.” {SchimincVs BericJii, 1923, p. 19).

“ Viscosity of Java Citronella Oil ” {ScJmnmcl’s B&richt, 1924,

CITRONELLAL. — Commercial cilroncllal is, according to the
latest researches, like citral, a mixture of two isomeric aldehydes,
of the formula CjoHigO. Of these the isomer corre.sponding with
citroncllol is citroncllal, and that corresponding with rhodinol is
termed rhodinal. Citroncllal is the chai'act eristic odour bearer
in Java citronella oil, and also in Ceylon citronella oil ; in both
oils it is mixed with gcraniol, the citroncllal predominating in the
former, and the gcraniol in the latter oil. Citroncllal is extracted
from citronella oil by means of its bisulphite compound in the
same wa.y as citral is prepared. The oil is fractionated and the
gcraniol recovered b^’’ means of its calcium chloride compound,
or by other suitable means, so that practically the whole of the
two constituents is recovered.

Citroncllal has a penetrating odour, but is only suitable for cheap
perfumery. It is, however, the raw material for the manufacture
of h 3 xlrox 3 ’'-citronellal {q.v.).

Commercial citroncllal is a pale 3 ^cUow or colom-lcss oil having
the following characters ; boiling point, 205° to 208° ; specific
gravity, 0-855 to 0-858 ; refractive index, 1-4450 to 1-4480 ;
optical rotation, + 9° to -}- 12°, occasionally slight^’- Irevo-
rotator 3 ’’if prepared from Java oil. Brins {Chem. ceJcMacl , 1917,
14, G92) gives the following characters for the isomers of
citroncllal (assuming the usuall 3 ^ accepted constitutions of
citronellol and rhodinol are correct) : Citroncllal — specific gravity,
0-888 at 14° ; boiling point, 203° to 204° ; and melting point of
scmi-carbazone, 85° to 80°. Rhodinal — specific gravity, 0-8745
at 14° ; boiling point, 198° to 199° ; and melting point of semi-
carbazonc, 83° to 84°.

Pure citroncllal is usually obtained b 3 ^ extracting the unchanged

154

PERFU MEE T

citroiiellal in the manufacture of citronellol from citronella oil
by means of sodium bisulphite.

CITRONELLOL. — Citronellol CjoHoqO is an alcohol found in
rose, geranium, and other essential oils. An acute controversy
-has for many years raged over the question of the relationships
between geraniol, citronellol and rhodinol. Ehodinol was put
xipon the market as a specific chemical individual diffeiing from
both geraniol and citronellol, by Ereneh chemists (Barbier and
Bouveault) ; various German chemists insisted that it was merely
a mixture of the other two alread 3 ’' well-knovTi alcohols. Bodies
named roseol and reuniol then appeared, but the most recent
work of Barbier and Loequin {Comptes Remind, 157, 1114) and
Harries and Comberg {Annahn, 1915, 410, 1) has praetically
settled the question, and roseol and reuniol, as well, probabl}'-, as
commercial rhodinol, m.a}’- be regarded as impure bodies. Com-
mercial rhodinol, however, has been shovm to contain an isomer of
citronellol, for which the name rhodinol has been retained. It
maj’- be taken for granted, therefore, that both citronellol and
rhodinol, as met vdth in commerce, are mixtures of the two
isomers. The following arc the characters of the commercial
articles which are usually obtained from citronellal bj’’ reduction,
and from geranium oil : —

From geranium oil,

Boiling point at 17 mm. . —

Boilmgpointat764mm. . 225°-22G°

Specific gravity . . 0'SG2

Refractive index . . 1’4570

Optical rotation . . — 1° 40'

Prom citronellal.

117°-118°

0-858
l'4yo5
+ 4°

Citronellol and rhodinol have faint but sweet rose odours,
and are used in the preparation of artificial otto of rose, where
it is usually associated with geraniol, phen 3 d-cth 3 d alcohol, oct 3 d
alcohol, dec 3 ’'l and nonyl aldeh 3 ’-des, traces of citral and traces
of phenyl-acetic acid, and various esters of geraniol and citronellol.
(See also “ Rhodinol.”)

The following is the usual method for the preparation of
citronellol by reduction of citronellal (Lewinsohn, P, ds E. 0. R.,
1923, 360)

Ten kilograms of aluminium turnings freed from grease by
washing in petroleum ether are treated with caustic soda solution,
and when hydrogen is briskly evolved the caustic solution is run
off and the metal washed with water. It is then treated for a
short time with 1 per cent, solution of mercuric cldoride. To

165

PERFU ME B.Y

9*3 kg. of aluminium so treated 54 kg. of 80 per cent, alcoliol and
18 kg. of citronellal are added, and then 0*45 kg. of mercuric
chloride. Eeaction commences at once, and the temperature must
he kept down to 35° by vigorous stirring and, if necessary, a water
jacket. The reaction mass, after sixteen hours, is diluted with
water and filtered, and then distilled, traces of citronellal being
removed from the citronellol by treatment with sodium bisulphite.

GITRONELLYL ACETATE.— This ester. C 10 H 1 yO.OC.CH 3 ,
is a natural constituent of geranium and rose oils, and is a useful
addition to most rose or geranium perfumes. Its odour recalls
that of bergamot oil. It is prepared by the acet 3 dation of
citronellol, and has the following characters : specific gravity,

0- 893 to 0-900 ; optical rotation, + 3° to — 3° ; refractive index,

1- 4450 to 1-4480 ; and boiling point, 120° at 15 mm.

GITRONELLYL BUTYRATE.— This ester, CioHigO.O.C.
C 3 H 7 , is prepared b}’' the suitable esterification of the alcohol.
It is a useful ester to add in traces to artificial rose perfumes. Its
specific gravity is 0-894, and refractive index 1-4465.

GITRONELLYL FORMATE.— By acting on citroiieUol with
concentrated formic acid, citroneltyl formate CiyHiyO.O.CH
results. Commercial samples rarcty contain more than 90 per
cent, of actual ester, as the reaction is incomjDlete. It is an oO of
sijecific gravity about 0-910, and refractive index 1-4510. It has
a faint rose odour with a suggestion of cucumber.

GITRONELLYL TIGLATE.— See “ Tiglic Acid Esters.”

GITRONELLYL VALERIANATE.— This ester has a fruity
odour. Its specific gravity is 0‘888 ; and refractive index 1'4435.

GIVET. — Of all the animal siabstances used in perfumery,
civet probabl}^ has the most revolting odour, closely resembling
fffices in this respect. In ver 3 ’' dilute solution, however, this
odour is not noticeable, and it is an extremely valuable fixative,
much appreciated for fine perfume work. It is a glandular secre-
tion of the civet cat. The foUovdng account of the natural
histoiy of this animal is due mainl 3 ’' to C. C. Treatt (P. cD E. 0. R.,
1912, 73. The civet cat tribe, the F? vendee, are confined to the old
world. In this tribe are included other closely allied carnivors
which do not produce civet, such as the mongoose and the
ichneumons. All the true civet cats possess two perineal glands,
forming a deep pouch in the posterior part of the abdomen, and
this pouch is divided into two sacs, each about the size of a marble,
in which the civet, secreted by the surrounding glandular foUicles,

166

PERFUMER Y

is stored. The civet iii the pouches is at first semi-fluid, but
becomes stiffer, and darkens in colour. The function of the civet
bag is not kuo^vn, but it is believed to be of value as a means of
defence on account of its foul odour, and also for the purpose of
sexual attraction. In spite of the foul odour, hounds will leave
any other scent if they once cross the trail of a civet cat. The
animals producing civet are the following ; Viverra zibetta, the
Indian civet of Bengal, China and Malaya ; F. civeUina, on the
Malabar coast ; F. incgaspila, the Burmese civet of Bimma,
Cocliin China, the Malay Peninsula and Sumatra ; F. iangalunga,
the Java civet of Java, Sumatra and Borneo ; and F. vialaccensis,
the rasse of India, Ceylon, Assam, Cliina, Java and Sumatra ;
and F. civcfla, the African civet cat. Almost the whole of the
world’s supply comes from the African civet cat. It is possible
that- the civet produced in other districts is used locally by the
natives. Although always wild, the animal will sometimes
become fairly tame in captivity, and the uniter (E. J. P.) has
freely handled a number of the cats, wliich showed no tendency
to bite. When, however, the civet is being collected, the cat is
cj^uite unsafe to handle. It is placed in a long cage in which it
cannot turn round, and teased and irritated, as the secretion is
much greater when the cat is angered. The civet is extracted
from the pouch -with a spatula, when it is pale yellow and semi-
liquid, but hardens and darkens on exposure to the air, becoming
rather stifier than butter. It is packed in ox horns, and protected
by a leather cap tied roimd the horn, and exported in these horns,
wliich usually hold about 30 oz. The bulk of it comes from
Abyssinia.

Civet is very frequently adulterated, the principal adulterants
being gummy and saccharine matter, banana pulp, or petroleum
jelly. Civet owes its odour to a mixture of skatol, possibly indol,
and a ketone termed zibethone, udth some free acids, ethylamine
and propylamine (Sack, Chem. Zeit., 1915, 39, 538). Zibethone
has the formula Ci 7 H 3 oO, and melts at 32-5°, boiling at 342° at
74r-mm.

A pure civet should have the following characters : —

Water .
klineral matter
Acetone exti’act
Dirt, hairs, etc.

Petroleum ether extract
acetone)

Alcohol extract (90 per cent.)

■ 167

6-10 per cent.

Not exceeding 2 p^ cent.
Not less than 80 per cent.
Not more than 5 per cent.

Not more than 6 per cent.
65-60 per cent.

PERFUMERY

The acetone extract should have an acid value of from 85 to
115, and the melting point should he from 42° to 4G°.

The alcohol extract should have an acid value of about 135,
and an ester value about 30.

The following characters for pm-e civet are given by Schimmel
& Co. {EericJU, 1924, lOG).

Acid value.

Ester value.

i ' —

Alcohol extract ....
Ether extract (after alcohol) .
Chloroform extract (after ether)
Residue

Water .....

For cent.
58

19-9

7*5

13-5

138-8

9-9

18-7

124-5

Adulteration with petroleum jelly causes a lowering of the
alcohol extract, and an increase in the ether extract, the latter, of
course, having a low ester value in the presence of petroleum jelly.

The following method will detect petroleum jelly in civet.
Five grams are well rubbed in a mortar with 50 c.c. of acetone,
until it is completely disintegrated. The mixture is allowed to
settle, and the clear liquid is poured off. The residue is well mixed
with another 50 c.c. of acetone and then poured on to a filter, and
the insoluble matter washed vdth a little more acetone. The
residue is now dried at a low temperature. If the civet be free
from petroleum jelly, it will be greyish-white in colour and
powdery, whereas if the adulterant be present, it will be oily or
pasty. In this case, the residue is well mixed vith 50 c.c. of
petroleum ether, the liquid filtered, and the insoluble matter
washed with more petroleum ether. In the presence of petroleum
jelly the filtrate will almost always be fluorescent (uifless the
petroleum jellj’’ has been completel}^ de-bloomed), and the solvent
can be evaporated and the adulterant weighed. A nucroscopic
examination should demonstrate the absence of vegetable cells
and fibres, wliich are present if vegetable pulps have been used as
adulterants.

Ai’tificial civet is a market article, but if^ entirely artificial
lacks much of the value of true natural civet. A mixtmre of
natural civet, however, "vvith synthetics, is more successful, and
the best “ artificial civet ” is so compounded. Skatol, indol, and
tetrahydro-pam-methyl-quinoline are the most useful sjmthetics
for the purpose.

168

PEBFUMEB 7

Niviere has published an account of his examination of civet
{Bull. Soc. Chim. (4), 1920, 27, 794), which is very illuminating
in indicating the results to be expected with adulterated civets.
Niviere examined four samples of civet described as pure.

Sample No. 1
„ No. 2
„ No. 3
„ No. 4

Insoluble in Benzene
(cold).

Per cent,

C'GO
6*40
7-00
, 18-35

Afeh

in same.

Trace

18*15 per cent.

The ash in sample No. 4 was talc.

After distillation of the benzene from the benzene extract in

a vacuum, the soluble residues were dissolved in 96 per cent,
alcohol. The amounts soluble in alcohol were as follows : —

Sample No. 1

„ No. 2

„ No. 3

,, No. 4

Per cent.

56*70'

57*01

55*21

38*82

Calculated on the
original weight
of the civet.

The acid numbers of the residues left after evaporation of the
alcohol in vacuo varied httle; from 103*1 (No. 1) to 111 (No. 4) ;
and the ester numbers varied from 15*3 (No. 1) to 25*2 (No. 4).

The author continued the examination only on sample No. 2,
as this presented the greatest probability of being pure.

The benzene insoluble part melted at 58° to 59°, and in it
cholesterine was identified mth certainty, and the following
results were obtained : —

Acid number
Ester number .
Iodine number .
Acetyl number .

8*4

69*7

68*43

80*02

_ These figures bear great resemblance to those furnished by
waxes.

Examination of the Alcoholic Extract. — ^The solvent was removed
in vaciw and the residue taken up with ten times its weight of
benzene. The solution at first was clear and limpid, but after a
few minutes it became turbid, and a deposit appeared. The
insoluble part was examined after, decantation. It was made up
of glucose, which was identified by its physical properties and its
osazone.

The acids present in the benzene solution were removed by a

169

PERFUMERY

5 per cent, solution of sodium carbonate, and constituted 0*35 per
cent, of the crude civet. Tliej'' are liquid at the ordinary temiDera-
tui’e, and then- odour suggests caproic and caprylic acids ; the
average molecular weight was 168.

After wasliing vdth water, the benzene solution was exhausted
with 5 per cent, sulphmic acid, and yielded skatol and some
volatile bases with an odour of ethylamine and propylamine.

After removal of the solvent, the remaining fraction, 57-2 gram
was fractionally distilled in vacuo, and yielded, at a pressme of

5 mm : —

Gr.

(a) 145°-180° .... 3-00

[b) 180°-200° .... 7-00

[d) 2]0°-220° . . . .20-80

(/) 230°-280° . . . .9 00

Residue ..... 9'00

Several of these fractions did not possess the characteristic
odour of civet : the}’' had the odom' of a fatty body somewhat
rancid. The fraction (cZ), which was solid, smelt Hlce rancid
stearme ; its meltmg f»omt was not very sharp, about 70° ; its
acid number, 198*4 ; and acetyl number, 160. It was, therefore,
chiefly made up of an acid containing hydroxyl, similar to those
present in -wool fat. Niviere concludes that this sample was
adulterated with lanohne, and probably liquid glucose.

CLARY SAGE. — Salvia Sclarea, Imovm as clary sage, or
muscatel sage, jdelds an essential oil the value of wliich cannot
be over-estimated for perfumery purposes. The plant is a native
-of the Mediterranean littoral, and has long been used by the
Itahans in the preparation of vermouth, and by the Germans
in giving wine a “ muscatel ” flavom,’. Gattefosse is mainly
responsible for having brought its great perfume value into due
prominence, and in 1909 he started its cultivation on a com-
mercial scale in the Vaucluse district. It flourishes best in the
warmer districts, such as Vaucluse, Basses-Alpes, Var, Alpes
Maritimes, Gard, Herault, and Ariege. It is commonly known
as muscatel sage or toute bonne. It prefers a light, stony soil.
It is usually cut tA’sdce a year, firstly in Juty, and, later, in
September. The first cutting is the richer in essential oil, the
second being usually dried as a herb instead of being distilled.
Propagation is usually effected by means of seeds, the 3’-oung plant

160

PERFUMER Y

growing to a height of about 1 8 inches in the first year, and 4 to 6 feet
in the second j^ear. The crude oil (or the substances extracted
bj’- means of a volatile solvent) has such a high fixative value,
combined with a useful odour, that it has become known in
Trance as huih amhrte, oil of amber, or vegetable ambergris. It
is an expensive oil, as the yield is quite small. In distilling the
oil lavender stills ma}'- be used, but rapid distillation with high-
pressure steam and higlil}’’ efficient condensation are essential.
When the plant is conveyed by road to the distillery, there is
usually a considerable time between the gathering of the plant
and its distillation, so that a certain amount of fermentation
takes place, and the product is less valuable than when distillation
follows the cutting immediately. If the wdiole of the plant be
distilled, including the roots, the oil may contain resinous and

District.

Esters,

Specific
gravity at 20®.

Rotation.

Refractive

indo:!C.

Nimes

Per cent.
72-0

0-983

- 11°

Vaucluse .

63-7

0-895

— 16-6°

Villeurbanne

62-75

0-897

— 22-1°

58-8

0-901

— 23-6°

1-4660

Lorgues

42-2

0-887

— 14-6

4o-l

0-898

—

0-898

—

JJ • •

66-7

0-894

—

oxygenated bodies of powerful odour. Tliis type of oil is useful
enough for fixative purposes, but is not of the delicate odour
necessary for the finest perfumery purposes. Where such an
oil is required, only the flowering tops should be distilled, W’-hich
are encouraged by liberal manuring. The character of the ofi.
varies with the state of matmity of the plant, the degree to which
the plant has been dried, and the time and weather when the
plant is cut. Tor example, a pure oil may contain as little as
38 per cent., or as much as 72 per cent, of esters, calculated in the
conventional manner as linalyl acetate. Tine oils, distilled only
from the inflorescences, are freed from resinous matter, wliich
is separated in the distillation and dissolved in inferior grades
of oil to be used solely for fixative purposes. The fine grades of
oil have an exquisite odour recalling neroli, bergamot, lavender-,
and ambergris. It can be used in nearly any type of fine perfume,

161

PEEF U M EE Y

1G0.J, when they were expelled bj* the Dutch. On the founding of
Penang by Captain Light in 1786 the East India Company tried
to break the Dutch monopoly, and the cultivation proceeded
slowly, but steadily, and Penang cloves are still amongst the
most highly esteemed, but the greater part of these are consumed
locally, so that a great deal does not reach the London market.

The word clove is derived from the French clou, a nail, from
the resemblance in shape of the dried bud to a nail.

The plant is generally grown from seed, but can also be propa-
gated by means of la3'crs. Seeds are soaked in water for several
da3’s, and when the3' have commenced to germinate the3’- are
planted out about G inches apart in shaded beds, with the bud
end above the ground. The plants are kept in these beds, well
.shaded and watered for nearly a 3*ear. When the3’’ are about
6 inches tall the shading is removed, and the3’’ are hardened off
by exposure to the sun for a month or two, and then planted out.
The most suitable soil is a dark loam with a substratum of dark
3^ellow earth mixed vuth gravel. In Zanzibar a red clay soil is
preferred. The tree onl3’’ grows successfully fairl3’’ near the coast,
and is said to require sea air. The clove tree commences to pro-
duce flower buds in the fourth or fifth 3'ear after planting, in
Penang and Zanzibar. In the Moluccas, this takes six to eight
years. The buds are read3’' for gathering in August to December,
in Zanzibar, and about a month later in the Straits Settlements.
In the ]\Ioluccas the harvest takes place twice a 3'ear, namely, m
Jul3’- and December. The buds are generall3^ l)icked off b3’' hand,
and are then spread out on mats to dry in the sun. In Ambo3ma
the3' are first dried on a framework over a slow wood fire, which
gives them a brown colour, and then are dried off in the sun,
when the colour changes to black. In Zanzibar, after the clove
buds are gathered, they are dried for six or seven da3’^s, during
wliich time they lose up to 60 per cent, of their weight. Zanzibar
cloves are smaller and more shrivelled, and of poorer colour, than
Penang and Ambo3ma cloves. The best cloves are large and
plump, but little wiinkled, and of a light purplish brown vdth a
purplish bloom on them. If gathered before they are ripe, the3'-
shrinlc and become shrivelled badly, whilst if insufficiently dried
they are liable to go mould3’’. For exhaustive details of the
cultivation and histor3’' of the spice, H. N. Ridley’s work “ Spices ”
(Macmillan, London, 1912), should be consulted. The flower
stallfs,- separated from the buds whilst they are df3dng, are also
dried and exported, and are distilled for their essential ofi, which is

163

11—2

PERFU MERY

present to the extent of about 6 to 7 per cent., as against 12 to
18 per cent, in the buds. These stems are known in France as
grijfes de girqfle. The dried fruits of the clove are known as
mother cloves ; these are occasionally exported, but are not.
usual articles of commerce.

Cloves are distilled to a very large extent, probably far in
excess of any other sj)ice. The oil is obtained to the extent of
12 to 18 per cent., sometimes even up to 21 per cent. It is used to
a certain extent in medicine, to a considerable extent as a flavour-
ing material, and on a verj^ large scale as a raw material in the
perfumery trade. A genuine clove oil has a specific gravity
1*044 to 1*070 ; optical rotation, — 0° 20' to — 2° 30' ; and
refractive index, 1*5290 to 1*5355. It contains from 78 to 98 per
cent, of eugenol.

Eugenol is the prmcipal constituent of the oil, and upon its
percentage the oil is valued. There are present also a small
amount of acet-eugenol, the sesquiterpene caryophyllene, traces
of eugenol ethers, vanillin, salicylic acid, methyl benzoate, am 3 d-
methj'l ketone, heptyl-methyl ketone, methjd-amjd carbinol,
methjd-heptjd carbinol, benz 5 d alcohol, and dimethjd furfurol.

The eugenol is extracted from clove oil b}^ absorption with a
solution of caustic alkali, from which it is set free on acidification.
A small quantity of eugenol is used as such in perfumer}^, in the
manufacture of clove and carnation odours, and a certain amount
is converted by heating with alkali, into its isomer isoeugenol,
which has a finer carnation odour, and is used for the same per-
fumes. The built of the eugenol so obtained, however, is used for
the manufacture of vanillin {q.v.), wdiich is used on an enormous
scale for chocolate flavouring, and to some extent also in per-
fumery. Eugenol is invariably determined in the oil, in practice,’
by means of an absorption with caustic alkali solution {vide
“ Phenols, Determination of ”), but the process devised by Thoms
is probably a little more accurate. (See E. J. Parry, “ The
Chemistry of Essential Oils,” 4th ed., vol. i., j). 333.)

The oil distilled from clove stems does not differ material^
from that of clove buds. A sample of the oil distilled from
mother cloves was found by Schimmel & Co., to have the following
characters: specific gravity, 1*053; optical rotation, — 3°11' ;
refractive index, 1*5433 ; and eugenol value, 88 per cent. Clove
leaves yield from 4 to 6 per cent, of an oil having a specific gravity
1*032 to 1*067 ; optical rotation, — 0° 30' to — 2° ; refractive
index, 1*5320 to 1*5390 ; and eugenol content, 75 to 93 per cent.

164

P B n F U 21 E B Y

The residue of clove oil fx'om the eugenol manufacture is used
as a cheap soap perfume imder the name “ light clove oil.”

COGNAC OIL. — Oil of cognac is used for flavouring, and,
to a small extent, in perfumer^-. The natural oil is obtained
during the ixrocess of fermentation of the grajxe juice bj’- the
j'east, and is prepared by distilling the residues of the vine used
for the production of brandy, or from the yeast cakes remauiing
after the removal of the vine. The development of the aroma of
Avine has been elaboratelj’’ investigated bj'^ Rosenstiehl {Compies
Bendus, 190S, 146, 1224, 1417 ; 1908, 147, 150). He found that
the partieular esters developed depended, not only on the character
of the grapes employed, but also on the miero-organisms that
develop on the fruit. The crude oil is usually of a greenish colour,
on account of traces of copper in combination vith free fatty
acids. If the copper be removed by shaking vith tartaric acid,
and the free fatty acids b}’- shaking AAith dilute caustic soda
solution, a purer oil is obtained. The physical characters of the
oil are very variable, and to a great extent depend on the degree
of rectification to which the oil has been subjected. The folloAving
values cover most genuine sainples : —

Specific gravit 3 '’ .
Refractive index
Optical rotation .
Acid value
Ester value

0- 870-0-890

1- 4270-1-4325

— 0° 30' to + 0° 45'
25-110
140-250

For the occurrence of traces of meth 5 d anthranilate in cognac
oil, see PoAver and Klleber, Jour. Agric. Besearch, 1923, 23, 47.

It was first considered (Pelouze and Leibig, Annalen, 1836, 19,
241) that the chief constituent of oil of cognac Avas the ethyl ester
of oenanthjdic acid, and that the latter was identical vith pelar-
gonic acid obtained from rose-geranium oil. Later investigations,
hov'ever, showed that oil of cognac is a mixtine of esters of ethji
and amyl alcohols and capric and caprylic acids (Eischer, Annalen,
1861, 118, 307 ; Grimm, ibid., 1871, 157, 264 ; Halenlxe and
Kurtz, ibid., 1871, 157, 270).

The term “ oenanthic ether ” is usually applied to the natural
product, but artificial esters are prepared which have an odour
resembling the true oil of cognac^ These are the ethyl esters of
cenanthylic and pelargonic acids.

OEnanthylic acid CH 3 (CH 2 ) 6 COOH is normal heptoic acid, and
is obtained by the oxidation of cenanthol, produced by the

166

PERFU 21 E R r

destructive distillation of castor oil. It is also formed by the
oxidation of normal lieptyl alcohol and of oleic acid, and by the
reduction of dextrose-carboxyhc acid. It is an oily liquid boiling
at 220° to 223°, and has a specific gravity of 0*918 at 20°.

QSnanthal, oenanthic aldehyde or normal heptylic aldehj'-de is
obtained by the dry distillation of alkaline ricinoleate. Castor
oil, wliich consists essentially of the glycerides of ricinoleic acid,
is rapidly distilled until a resinous residue remains, the greater
part of the ricinoleic acid being converted into cenanthal and
higher fatty acids. The distillate is rectified and the portion
distilling between 90° and 180° shaken with- a saturated solution
of sodium bisulphite, warmed, and filtered. The salt, which
separates on cooling, is pressed between filter paper, mixed with
sodium carbonate, and distilled in a current of steam. The
cenanthal wliich floats on the distillate is separated and dried over
anhydrous sodium sulphate. A better yield is obtained by
distilling the ethyl or methyl ester of ricinoleic acid.

Ethyl pelargonate is prepared by the action of dilute nitric acid
on oil oT rue. The oil is treated vfith tvdce its weight of dilute
nitric acid and heated until the mixture begins to boil. Two
layers are formed, the upper one containuig the cliief produets
of oxidation. The lower layer is freed from nitric acid by heating
on a bath containing a solution of zinc chloride. The two liquids
are then filtered, and the pelargonic acid is converted into the
ethyl ester by esterification with alcohol, and purified by steam
distillation.

CONCRETES. — See “ Extraction of Perfume from Plants.”

CONV ALLARIA MAJALIS. — ^This is the lily of the valley.
The perfume is prepared in the form of a concrete or absolute,
but as found in the market is mainly synthetic. (See Lily ”
and “ Muguet.”)

CONVOLVULUS OIL. — ^The wood of Convolvulus scopavius
and G. floridus, both indigenous to the Canary Islands, yields a
small quantity of essential oil, which is the true rosewood oil, or
oil of rhodium. It is a liquid which sohdifies at low temperatures,
melting again at 11° to 12°. Its general characters are not known
with certainty, as the authenticity of most samples examined is
doubtful. The oil as met with in commerce is almost entirely
an artificial mixtiu’e. It is used in soap perfumery, and must not
be confused with the oil of Bois de Rose.

166

PEBF U JI E li r

CORIANDER, OIL OF.— This oil, occasionally used in per-
fumery, for example in traces in eau de Cologne, is distilled from
the rijje fruits of Coriandrum sativum, a native of the Levant and
southern Europe. The oil contains dca-h’o-linalol, pinene, and
other constituents not j^et identified. It has a specific gravity
0-S70 to 0-885 ; optical rotation, -f- 7° to -f- 14° ; and refractive
index, 1-4035 to 1-4760. (For the liistory, etc., of tliis spice, see
Eidlej", “ Spices,” p. 384.) Indian distillates sometimes have a
refractive index as low as 1-4569.

CORIANDROL. — ^An old name for impure linalol when
extracted from coriander oil.

GORYLOPSIS. — ^The Japanese plant Corylopsis spicala
bears highly odorous flowers which have a heavy, somewhat
sickly odour, Iflce that of many orchids or lilies. The perfume is
not extracted, but the name is applied to fancy perfumes wliich
have some slight resemblance to the natural odour. These are
usually based on infusions of rose, jasmine, tuberose and orange
flowers, with the addition of a little vetivert or patchouli oil,
hydroxy-citronellal, terpineol, ylang-jdang oil, and a trace of
artificial essence of strawberry.

GOUMARIN. — Coumarin is one of tlie most important of the
artificiaUj'- prepared perfumes. It is the substance to which the
Tonquin bean (Tonlca bean) owes its odour ; it is found in
appreciable quantity in the leaves of the American “ deer’s
tongue,” Lialris odoraiissima, and has been found in a large
number of other plants in smaller quantity {vide E. J. Parry,
“ The Chemistry of Essential Oils,” 4th ed., vol. ii., p. 272).
Commercial coumarin is invariably the artificial product. It was
first prepared synthetically by W. H. Perkin {Chem. Soc. Jour.,
xxi., 53, 181) by heating salicylic aldehyde (q.v.) with acetic
anliydride and sodium acetate. Tiemann and Herzfeld heat

3 parts of salicylic aldehyde, 5 parts of acetic anhydride, and

4 parts of fused sodium acetate on an oil bath for twenty-four
lionrs. Water is then added, and the oil which is precipitated is
separated. This consists of acetyl-or/7io-coumaric acid, with a
little coumarin. This acid is decomposed by heating it to a little
below its melting point (146°) into acetic acid and coumarin.
RascHg first prepares oriZjo-cresol carbonate by the action of
phosgene on or^^o-cresol in the presence of pyridine. A current
of chlorine is passed through this ether at 180°' which results in
the formation of di-chlor-o-cresol carbonate. On hydrolysis this

167

PE B F U 31 E B Y

yields salicjdic aldeh 3 ’^de, from which coumarin is prepared as
above described. Hugo Weil has patented a method depending
on the reduction of salicyhc acid by sodium amalgam in the
presence of boric acid. The sahcyhc aldehyde is, as it is formed,
combined with paratoluidine. For example, 15 parts of salicyhc
acid, 5-5 parts of sodium carbonate, 1,000 parts of water, 18 parts
of toluichne, 250 parts of salt, and 15 parts of boric acid are mixed
and treated with 325 to 425 grams of a 2 per cent, sodium amalgam.
The liquid is kept acid by the addition of boric acid. The ortho-
oxj^-benzylidene-paratoluidine is filtered off and dissolved in a
faintly acid solution which, on steam distillation, jdelds sahcyhc
aldehj'^de, which is converted into coumarin in the usual
manner.

Coumarin is a highly odorous substance melting at 68 °, and
havmg the characteristic odour of Tonquin beans. It is a basic
material for aU perfumes of the t 5 qoe of foin-coupe, or “ new-mown
bay.”

It is often adulterated with acetamhde and with terpin hj’^di’ate.
The former is detected bj^ heating the sample with a solution of
caustic potash and adding a few drops of chloroform, when, on
boilnig, the intense odour of phenjd isoc^’^anide is evolved. Terpin
liydrate is recognised bj^^ boiling the crystals with dilute sulphuric
acid, when the odour of terpineol is at once noticed.

CRATEGINE. — This body is identical vdth anisic aldehyde,
either pure or in a reduced condition.

CRATEGUS OXYCANTHA. — See “ Hawthorn.”

CREOSOL.— This body is a diphenol, C 7 H 6 (OH) 2 , occurring
in oil of ylang-ylung. It is an odorous oil, boiling at 220°.

CRESOL (META-). — This body is a cr 3 ’’staUme substance of
the formula C-HgO, melting at 4°, and boihng at 201 °. It ocem’s
to a small extent in essential oil of myrrh. It is used in the
manufacture of artificial musks. It is a colourless liquid of
specific gravity 1-0375, cr 3 ^stallising at 10° to 12°, and boiling at
202° to 203°.

CRESOL (PARA-) . — ^This bod 3 ’-, isomeric vdth ?7ieto-cresol
C^HgO, is a crystalline body melting at 36°, and boiling at 199°.
It is found in the oils of jasmin and cassie flowers.

CRESOL (PARA-) BUTYL ETHER.— This ether, C 7 H 7 .
O.C 4 Hg, is prepared by the condensation of pam-cresol and but 3 d

168

PE BFU 31 E P y

alcoliol by means of lij’drocliloric acid. It is useful in the prepara-
tion of artificial ylang-ylang and similar odours.

CRESOL (PARA-) METHYL ETHER.— This body, of
the formula CyH^.O.CHg.-is a natural constituent of ylang-ylang
and other flou'er oils. It is a colourless liquid, darkening on
keeping, with a powerful odour, which recalls that of wallflower,
on dilution. It boils at 175°, and 3 delds anisic aldehj'de on
oxidation. It is essential for the production of artificial flower
oils of the jflang-jdang and wallflower t 3 ’’pes. It is prepared
artificiall 3 ^ b 3 '’ condensing poru-cresol with methyl alcohol by
means of h 3 'drochloric acid. Its specific gravit 3 ’ is 0-f)75 to 0-977,
and refractive index 1-5130.

CRESYL (META-) PHENYL ACETATE.— This body is
isomeric vith the corresponding para-cres 3 d derivative. It has a
sweet, heav 3 ’- odour, and is useful in the preparation of 3 dang-ylang
and other exotic floral perfumes.

CRESYL OXIDE. — There are three cresyl oxides, correspond-
ing with the three isomeric cresols. The 3 '^ have the formula (C 7 H 7 ) 20 .
The best knovm is the di-o? 77 io-cres 3 d oxide, which boils at 275°.
It is prepared b 3 ’’ dehydrating cresol, or by distilling cres 3 date of
aluminium, or by condensing bromotoluene with cres 3 date of
potassium in the presence of finely powdered copper. It is useful
as a variant of phen 3 d oxide in the preparation of artificial
geranium perfumes.

CRESYL (PARA-) ACETATE. — This acid ester of cresol
CH3.COO.C7H7 is prepared by the interaction of ^ora-cresol and
acetic anh 3 ’'dride, or of the sodium compound of the phenol and
acet 3 d chloride. It has been known as narceol. It has a powerful
narcissus odour. It has a specific gravit 3 '’ 1-0528, and refractive
index 1-5040.

CRESYL (PARA-) PHENYL ACETATE.— This body is
of , a sweeter narcissus odour than the corresponding acetate. It
has the constitution CeH 5 .CH 2 COO.C 7 H 7 .

CROPS, TIMES OF FRENCH FLOWERING.— The

usual times at which the more important of the French flowers

are gathered for treatment are as follows : —

February-IIarcJi : . Cassie, violet, mimosa, hyacinth.

Ax>yil .... Jonquil, h 3 ^acirith, narcissus, violet,

carnation.

1G9

P Eli F TJ 21 E R Y

Hay .

June .

J uly .

August-Septemher
October— N overnber

Jonquil, narcissus, orange flowers, rose,
rosemary, thyme, broom, carnation.
Kose,_petitgrain, mignonette, carnation.
Jasmin, lavender, rose, rosemary
thyme, tuberose. ’

Tuberose, lavender, jasmin. . '

Cassie, jasmin.

GULILAVAN OIL.— Culilavan oil is distilled from the bark
oi Cmnamomum Culiaivan. It is an oil of specific gravity l-OSO
o -055, ai;d contains about 60 per cent, of eugenol, with a small
quantity of methyl eugenol and terpineol.

hvde^^H This body (p-isopropyl benzaldo-

njae UigJliaU) is a natural constituent of cassie flower oil, but is

foimd to a much larger extent in cummin oil. It has a powerful
odour, and should only be used in traces in floral perfumes It
has a specific gravity 0-982, and boils at 236°

CUNNINGHAMIA SINENSIS —This tree, ' growing in
lonkm, yields a^ wood which is known as “ coffin wood,’’ or
^ san-mou. ’ This is used to make coffins which are said to be
mdestructible, joss sticks, and other preparations for burnino-
Gardies (La Parfumerie Moderne, 1923, 110) has examined the
essential oil, which has an odour of terpineol and cedrol, and found
it to have the following characters : specific gravity, 0-957 •
optical rotation, — 23° 6' ; refractive index, 1-4932 ; esters'
7-4 per cent. ; and free alcohols, 29-4 per cent.

CUS-CUS. — See " Vetivert Oil.”

CYCLAMEN.— There is no natural perfume extracted from
the cyclamen as a commercial article. Various species of perfume-
bearing plants are found growing wdld in the Alpine regions, of
which Cyclamen persicum is one of the sweetest scented The
odour of the flowers is of the amaryUis or lily type, and is
matched, to some extent — but only as a fancy perfume which
does not, in fact, reproduce the odom’ of the flower — ^by the use
of hydrox3’^citronellal, ionone and phenyl-acetic aldehyde, vdth
traces of terpineol, and some weak floral basic perfume such as

cinnamic alcohol. A trace of acetic ether gives tone to this
perfume.

CYCLOGERANYL ACETATE. — This ester C10H17.COO.CH~
does not^ occur naturally. It is prepared by the action of
phosphoric acid on geranyl acetate at a low temperatiire, and by

170

PERFUMERY

then dehydrating the glycol so formed by means of phosphoric
acid at 40°. It is an ester with a sweet odom' of fresh flowers.

CYMBOPOGON OILS. — See under Citronella, Lemongrass,
Palmarosa, and Gingergrass Oils. Also “ Cymbopogon Nervatus,
Oil ofj” etc., and under Grasses (Perfumed) of India and Cejdon.”

CYMBOPOGON GAJSIUS.— This grass is closel}' allied to
C. Martini, but is distinctly different. Where the two grasses
meet, transition foi'ms occur in which the two species unite
completely*. Pew details as to the oil ai’e available. (See Adminis-
irafive Rej}ort of the Government Botanic Gardens and Parks in the
Nilghirisfor 1901, ji. 5. See “ Iniclii Grass.”)

CYMBOPOGON COLORATUS. — Samples of the oil dis-
tilled from this grass in the Fiji Islands examined at the Imperial
Institute (Bull. Imp. Inst., 1912, 10, 27) were found to have the
following characters : specific gravity, 0-911 to 0-920, and optical
rotation, — 7° to — 11°. One sample contained 40 per cent, of
aldehydes, principally citral, 23 per cent, of geraniol, and 10 per
cent, of esters, piincipally geranyd acetate. A second sample
contained 15-6 per cent, of geraniol, and from 45 to 50 per cent,
of citronellal.

CYMBOPOGON JAVANENSIS.— This grass yields a
highly aromatic essential oil with a sweet odour, resembling
palmarosa oil. It has been examined by Hofman (Pharm.
Werkhlad, September 6th, '1919). It had a specific gravity 0-975 ;
optical rotation, — 3° ; refractive index, 1-5135 ; acid number,
1-25 ; geraniol content, 4S per cent. ; esters, 14-3 per cent. ; and
methyl-eugenol, 30 per cent. Citral, Zeero-pinene and methyl-
isoeugenol are also present in the oil.

CYMBOPOGON NERVATUS.— This plant is the Naal
grass, found very widely distributed in the central portions of the
Sudan, being abundant in the Blue Nile, Fung, and Kordofan
provinces. The grass, when collected in full fiower, in the autumn,
yields the highest amount of oil— varying from 0-8 to 1-5 per
cent, of the weight of the dried grass. The infiorescence alone
is of value for distillation, as the stalks contain very little' oil.
The oil was reported upon by ScJdmmel cO Co. (Report, April,
1911, 19), but from details published by Joseph and Whitfield
(P.' c& E. 0. R., 1922, 175), it is probable that the oil they examined
was not a genuine one. The oil obtained by these chemists was
pale yellow in colour, and in odour closely resembles gingergrass

' 171

P B P F U M B R Y

oil — the so-called “ Sofia oil " distilled in India from Gymhopogon
Martmi. Three samples had the following characters :

20°

Specific gravity at ^ . . . j

0*954

0*955

0*953

Refractive index

1*495

1*492

1*495

Optical rotation ....

— 31° j

I — 35°

— 50°

Acid value .....

3*6

.4*4

Ester value .....

29*6

21*8

26*5

Ester value, after acetylation .

198

189

Naal oil contains Zcez/'O-limonene and porillic alcohol.

CYMBOPOGON POLYNEUROS.— This grass, growing
freely in Ceylon, ^fields an odorons essential oil having the
following characters : specific gravit}’", 0*936 to 0*951 ; optical
rotation, -f 31° to -{- 53°, and containing 38 to 52 per cent, of
aromatic alcohols.

GYPERUS ROTUNDUS, OIL OF.— Joseph and Whit-
field {videP. cb B. 0. i?., 1922, 176) have described this oil, which
is known as Seid oil. The plant grows in the Nuba Mountains
province, about twenty nules to the east of the White Nile, and
about 350 miles south of Kliartoum. The plant, which is a sedge,
gTows freely in the Sudan, and the rliizomes yield 0*5 per cent.

an aromatic essential oil, of specific gravity at

20 °

2 ^’

0-955 ;

optical rotation, — 20° ; and iv3fractive index, 1*4967 at 25°.

CYMBOPOGON SENNAARENSIS, OIL OF.— The so-
caUed mahareb grass of the British Sudan yields about 1 per
cent, of a fragrant essential oil, wliich somewhat recalls penny-
royal. Roberts {Jour. Gli&rn. Soc., 1915, 1465) states that it has a
specific gravity 0*938 to 0*942 ; optical rotation, -f 29° to -f 34° ;
and ester value after acet 3 dation, 60 to 62. The oil contains
pinene and limonene, menthenone, a sesquiterpene alcohol, an
alcohol of rose-hlce odom-, higher fatty acids in the form of esters;
traces of a phenol, and one or more sesquiterpenes.

CYMYLACETIG ALDEHYDE.— This body (l-isopropyl-4-
ethanal-benzene), of the formula (CH 3 ) 2 .CH.C 6 H 4 .CH 2 .CHO, is
obtained by the condensation of magnesium cymyl chloride with

172

PEEFUMEB T

ethyl orthofoimate, hydrolysing the product -ndth dilute sul-
phuric acid, and separating the aldehyde by means of its bisulphite
compoimd. It is a pale yeUow liquid, boiling at 243°. It has a
strong verbena bdoitr, and may find emploj’^ment in sjoithetic
perfumery (Best, Comptes Eendns, 1923, 550).

DACRYDIUM FRANKLINII, OIL OF.— The leaves of
Dacrydnim Franklinii, which grows only in Tasmania, where it
is known as the Huon pine, jdeld 0-5 per cent, of essential oil
having the following characters : —

Specific gravity .... 0-8677

Optical rotation , . . .4-20*5°

Refractive index . . ' . . . 1-4835

It consists mainly of terpenes, but there is also present a small
amount of methyl-eugenol.

The wood yields about 0-5 per cent, of oil having the following
characters : —

Specific gravity at 18°
Optical rotation
•Refractive index at 23°
Acid value
Ester value

1-035-1-044
4- 0-6° to 4- 1-4°
1-5316-1-5373
0-9-3- 1
1-5

■ This oil consists almost entirely of methyl-eugenol. It has
recently been examined at the Imperial Institute {Btdkiin,
vol. xxii., No. 3, 1924) and the following results recorded : —

Specific gra-vdty at 1.5/15° C.

1-040

Optical rotation aD .

. - 3-75°

Refractive index nD .

1-533

Acid value

0-8

Ester value before acetylation

0-9

Ester value after acetylation

. 11-2

Solubility in 70 per cent, alcohol

. Soluble in

1-5 vols.

On distillation, about 90 per cent, of the

oil passed over between

250° and 253° -under 755 mm. pressure, and consisted essentially
of methyl-eugenol. The results of the investigation show that
the composition of the present sample of Huon pine oil agreed
with that recorded for the oil by previous observers. Methyl-
eugenol is used to some extent in perfumer}’-, ■ but no regular
demand has hitherto arisen for Huon pine oil, although it is clear
from the results of the inquiries made by the Imperial Institute
that there is likely to be a demand for it if it can be supplied in
commercial quantities and at a reasonable price.

173

PEBFU MEB r

DAFFODIL PERFUMES. — These are inerety rariations of
narcissus odours, or, in fact, often identical except in name.
{Vide “ Narcissus.”)

DALBERGIA GUMINGIANA, OIL OF.— According to
Boorsma [Bull, du Dip. d' Agricult, aux hides Neerl., 1907, 7, 25),
the wood of Dalbergia Cuiniiigiana, which is found in Dutch
East Indies, yields about 0-5 per cent, of an essential oil of
aromatic odour having the following characters : —

Specific gi’avity at 26° . . . 0-891

Optical rotation . . , , — 4° 31'

Ester value ..... 5

Ester value after acetylation . . 116

The wood is known localty as Tcagii laha.

DARWINIA OILS. — The essential oils of several species of
Danvinia, growing' in Australia, have been found to have distinct
perfume value. They have been investigated by Baker and
Smith {Jour, ds Proc. Boyal Society Neiv South Wales, 1899, 163
and 1916, 181). The oil distilled from Darwinia fascicularis, a
shrub found in the neighbourhood of Port Jackson, was obtained
to the extent of 0-45 per cent. It has a specific gravity 0-916,
is slightly dextrorotatorj’-, and contains from 55 to 63 per cent, of
geraniol, mostly in the form of geranyl acetate. The oil from
Darwinia iaxifolia has a specific gravity 0-876, and an optical
rotation — 6-6°. It contains a small amount of an alcohol, which
is probably linalol. The oil from Darwinia grandiflora (originally
knoAvn as D. iaxifolia, var. grandiflora) has been examined by
Baker and Smith, and more recently by Penfold [Jour, and Proc.
Boyal Soc. N.S.W., Ivii., 237). The oil has a specific gravity
from 0-901 to 0-9165 ; and optical rotation, + 18-26° to -j- 27-65°.
The oil contains dea;/?*o-pinene, a sesquiterpene alcohol, and esters
of an alcohol which has, provisionally, been named darvdnol.
This body has the formula CjoHigO, and possesses the foUovdng
characters : —

Boihng point at 10 mm. 108° to 111°

Specific gravity . . O’ 955 9

Optical rotation . . + 38’6°

Refractive index . . 1-4918

DAUCUS, OIL OF. — ^The seed of the common carrot
{Daucua Caroia), yields an essential oil which has a distinct
perfume value. The jdeld is from 1 to 1-5 per cent., and the oil
has the following characters : specific gra’vdty, 0-870 to 0-946 ;

17d

PERFUMER J

optical rotation, — 11° to — 40° ; refractive index, 1'4S20 to
1-4920 ; and ester value, 17 to 55. The oil contains terpenes, and
a divalent sesquiterpene alcohol, C15H26O2, melting at 115° to 11G°,
and which has been named daucol. Roure-Bertrand Fih {Bulletin,
April, 1912, 30) have examined the oil distdled from the entire
plant at the period of maturity of the seed, and found it to have a
specific gravity 0-902 ; optical rotation, — 7° ; and saponifica-
tion, 195. The essential oil of the closelj’’ sBiod DaucusGingidium
has a rather finer odour* than the ordinary carrot oil. It is prac-
tically identical in general characters with carrot oil, containing
daucol as its odorous constituent. The oil has an odour recalline
that of orris oH, and is of great value in toning dovui the some-
what crude odour of pure ionone and similar synthetic violet oils.

DECALEPIS HAMILTONII. — ^By the steam distillation of
the crushed fresh roots of Decalejns Ilamiltonii, a plant used
cliieflj’- as a condiment in hfysore, a bromnsh solid substance has
been obtained which crj’-stallises in the condenser. Treated rvith
a little animal charcoal and redistilled, it forms a pure white
crystalline body melting sharply at 41°. It is probablj’- identical
with the crystalline body isolated by Goulding and Pelly {Proc.
Cliem. Soc., 1908, 62, 1911, 235) fi'om a species of chloroeodon
roots. It has an aromatic odour similar to that of vanfilin.

DEGINE CARBONATES.— See “ Heptine Carbonates.”

DEGYL ALCOHOL.— This alcohol, CH3(CH2)8CH20H, is
the most useful of the higher fatty alcohols {vide “ Alcohols,
Higher Fatty ’'). It melts at — 10°, and boils at 231°. It is
exceedingly useful for giving a new tone to fioral odours. Its
specific gravity is 0-833.

DEGYL ALDEHYDE. — See “ Aldehydes, Higher Fatty.”

DEMENTHOLISED PEPPERMINT OIL.— See “ Pepper-
ment Oil.”

DEODAR. — See under “ Cedarwood Oil.”

DEPILATORIES. — These substances rank among the less
dignified articles included in the perfumer’s art. Comparatively
large quantities are exported to the East, and many women in the
West elect to risk damage of a disfiguring nature to their skins
for the sake of removing superfluous hairs. Alkaline sulphides are
the basis of many of these preparations, calcium hydrosulphide,
strontium hydrosulphide, sodium sulphide and barium sulpliide
being those principally used, frequentty in admixture with

175 •

PEBFU MERY

powdered quicklime, and diluted uitli starch, sugar or talc.
These preparations convert the hairs into a gelatinous mass, but
only attack normal skins after repeated employment, Rushma,
a favoiu'ite preparation in the Eastern harems {vide Durvelle,
“ Perfumes and Cosmetics,” p. 313) is essentially a preparation
of arsenic sulphide (orpiment) and lime with a httle sulphur.
Thallium acetate, in combination with zinc oxide, has been
recommended as a depilatory ; it appears to be ver}’- powerful,
but not to attack the roots of the hair, so tliat its effect is quite
temporary.

DEVARDARI OIL. — ^The wood of Erylliroxijlon mono-
gynum, the so-called bastard sandalwood of India, yields about
0-25 per cent, of an odorous essential oil having the following
characters ; specific gravity, 0*983 ; ojJtical rotation, + 16° ;
refractive index, 1*5140 ; and containing about 40 per cent, of
a sesquiterpene alcohol. The oil has a sandalwood odour, and is
of use in cheap perfumery where tliis odour is required.

DHELUM WANGI. — ^This plant, also known as Tilam
wangi or Dilem icangi, is the true patchouli, under cultivation,
as a rule, for distillation pinqooses. DJiclv.m ouian is a wild
patchouli, of unknomi botanical origin, which is sometimes added
to the true leaves for distillation, {Vide “ Patchouli Oil.”)

DIACETINE. — This is an artificial ester, or a constituent of
commercial triacetine, which is used for adulterating ester-con-
taining oils. It is a practical^ odourless body, having a specific
gravit 3 '’ 1*184, and boiling point 260° to 265°. One part of this
body indicates 2*22 parts of esters returned as linaljd acetate.
{Vide “ Esters, Artificial.”)

DIAGETYL.— This body is a diketone, CH3.CO.CO.CH3, found
in the distillation waters of sandalwood, orris, savin, carawaj’’, and
various other essential oils. It has a specific gravity 0*9734, and
boils at 87° to 88 °.

DIANTHUS PERFUMES.— See “ Carnation.”

DIGITRONELLOXIDE. — Java critonella contains a com-
pound, C 20 H 34 O, which Spornitz {BericMe, 47, 2478) has named
dicitronelloxide. It boils at 182° to 183° at 12 mm., has a specific
gravity, 0*920 at 20° ; optical rotation, — 4° ; and refractive'
index, 1*4918.,

DIGTAME BLANG, OIL OF. — ^The oil known as essence
de diciame Wane oit calament, which was distilled in Oran, Algiers.

176

PEBFU MEB Y

]:es lecn examined by Schimmel cO Co, (Beport, October, 1906, 84).
It is in all j'rcbabilit}’' derived from Amaracus dictammis, one of
the Labial (E, The oil is of a pale strav yellow colour, with a
strong odour of pulegone, which is present to the extent of about
85 per cent. The oil has the following characters ; —

Specific gravity

0-935

Optical rotation

. -f 6°

Acid value ....

2-3

Ester value ....

. 20-9

Ester value after acetylation

. 80

It probablj' contains borncol and menthol.

DIGYPELLIUM GARYOPHYLLATUM, OIL OF.— The

bark of Dicj/j^elU'inn caryophyllatuin, one of the Lauraceoi, found
in Bi’azil. jdolds about 4 per cent, of a pale yellow oil having a
pow’erful odour of cloves and containing much eugenol.

DIETHYL SUGGINATE.— See “ Ethyl Succmate.”

DIHYDROGARVEOL.— Dihydrocarvcol, CjoHigO, is a natural
constituent of caraw^ay oil, and may be prepared by the reduction
of carvone. It is an oil of agreeable odour, which, when pre-
pared in as j)ure a state as possible from caraw^aj’’ oil, has a
specific gravity, 0-937 ; optical rotation, — 6° 14' ; refractive
index, 1-4S3G ; and boiling point, 225°. Prepared artificially
by treating 20 grams of carvone in 200 c.c. of absolute alcohol
wdth 24 grams of sodium, it has a specific gravity 0-927 at 20°,
and refractive index 1-4817. It exists in both optically active
varieties, according to the optical activity of the carvone from
which it is prepared.

DIHYDROGARVEOL AGETATE.— This ester has been
identified in American oil of spearmint.

DIHYDROGARVONE.— This ketonic compound, of the
formula CioHigO, is found to a small extent as a natural constituent
of caraw^ay oil, and is prepared artificially bj’- the oxidation of
diliydrocarveol by means of cliromic acid in acetic acid solution.
It is an oil having an odour recalling that of menthone and car-
vone, and has the following characters : specific gravity, 0-930 ;
boiling point, 222° ; refractive index, 1-4711 ; and optical
rotation, — 16°.

DIHYDROGUMINIG ALGOB-Oh.— Schimmel cO Go. {BericJit,
April, 1904, 53 and October, 1904, 41) isolated an alcohol from

p 177 12

PE BF U M FRY

gingergrass oil' wliicli boiled at 226° to 227°, and had a specific
gravity, 0*951 ; optical rotation, — 13° 18' ; and refractive index,
1*4963. Tliej’’ termed this dih 3 ’'drocuniinic alcohol. It had an
odour recalling that of a mixture of linalol and terpineol. It
has now, however, been shown by Semmler and Zaar {Bericlite,
44, 460) to be identical vdth perillic alcohol {q.v). Elze {Clmn.
Zeit., 1910, 34, 1175) has claimed more recently to have isolated
15 per cent, of the true dihydrocuminic alcohol from German oil
of spearmint. This had a specific gravity 0*9539 ; and optical
rotation, — 30° 15'. It yielded a naphtltyl-urethane melting at
146° to 147°, and when oxidised jdelds an aldehyde, cUliydro-
cuminic aldehyde, which forms a semicarbazone melting at
198° to 199°. These figures are so close to those of the correspond-
ing ones for perillic alcohol as to make it probable that Elze’s
body is also identical with the last named, and is not dihydro-
cuminic alcohol.

DIHYDROCUMINIC ALDEHYDE.— The essential oil of
the wood of Hermmdia peltata contains, according to ScJmnmel c&
Co. [Bericht, April, 1915, 54), this aldelij'de, CioHj^O. The same
body is present in the oil from the leaves of Pcrilla arguta, a
Japanese oil known as Shiso, and is now known as perillic aldehyde,
and as its constitution is apparently decided, and is not that of
dihydrocuminic aldehyde, it is probable that the latter does not
actually exist in the essential oils mentioned.

DIHYDROFARNESOL.— Verley {Bull. Soc. Ghim. 1924, 35,
606) claims to have synthesised a new sesquiterpene alcohol,
wliich he names diliydrofarnesol. It is an amber-coloured oil
having an odour resembling cedarwood. Its constitution is
CHa : C(CH3)(CH2)3.C(CH3) : CH(CH2)2CH(CH3)CH2.CH20H.

Earnesol is oxidised to farnesal, and tliis is converted into a
glycidic ester, which on reduction jdelds dih^^'drofarnesol.

DIHYDROIONONE. — ^The isomeric ionones jdeld two dif-
ferent dihydroionones on reduction. These bodies are of no
practical importance in perfumery, but are of great value in
establishing the identity of the isomeric ionones (g'.'W.).

DIHYDROXYTHYMOQUINONE.— This body has been
found in the essential oil of Monardafisiulosa by kliller {Circular 4,
1918, University of Wisconsin).

DILEM OIL. — A name given to Java patchouli oil. (See
" Dhelum ” and “Patchouli.”)

178

PEBF U ME R I

DILL-APIOL. — This body is a constituent of East Indian,
Spnnisli, and Japanese dill oils. It is isomeric with ordinal}^
parsk-;\' apiol, differing from it only by the relative

jioshions of the side chains. It boils at 285° ; has a specific

13=

gra.vitv. T1G4 at ; and refractive index. 1-5278 at 25°. Iso-

dill-apiol, a second isome]' of ordinary apiol. is found in the essential
oil of Piper acntifolhnv .

DILL, OIL OF. — The essential oil distilled from the seed of
Av.c'Jmm gravcolcns is known as oil of dill. The plant is indigenous
to central and southern Europe, but is found in many other
localities. A plant growing largely in India has been described
as AnetJium soica, but the botanical difference between the plants
is not yet settled. The odour of dill oil is similar to that of caraway
oil, with, however, a distinct difference. It is a mixture of
limonene and carvone, mth traces of other bodies, but the carvone
is present in less amount than in caraway oil. European diU oil
has the foUovdng characters : —

Specific gravity . . ' . 0-895 to 0-918

'Optical rotation . . . 70° to -f 83°

Refractive index . . . 1-4830 to 1-4900

Carvone . . . . 30 to 60 per cent.

Indian dill oil always has a much higher specific gravity, this
figure usualty varying between 0-945 and 0-970. Its optical
rotation is + 40° to + 50°. This oil contains a body, C12H14O4,
isomeric with ordinary apiol from parsley oil, and which has been
named dill-apiol. J. C. Umney (P. tf? E. 0. R., 1910, 290) has
examined an African dUl oil which was distfiled fi’om plants grovm
from Enghsh seeds. Its characters were substantially identical
vffth English oil. Japanese dill oil appears to be produced from
the same seed as the East Indian oil.

DIMETHYL-BENZYL CARBINOL.— This body,
CH2.C(0H)(CH3)2, is an isomer of phenjd propyl (hydrocinnamyl)
alcohol. It forms crystals melting at 21°, and boiling at 225°.
It is prepared by the interaction of zinc methide and phenylacetyl
chloride. It has an odour recalling that of narcissus, hj’^acinth
and lilac, and is one of the rarer, but higlil}’' prized, sjmthetic
perfumes.

DIMETHYL-HEPTADIENE-OL.— This body is one of
most recentty synthesised odorous compounds, formed by the
condensation of mesityl oxide and bromopropyl acetate. It is an

'179

P E BE V M E R Y

oil, boiling at 78° to 80° at 18 mm. It jDOSsesses an intense odour
of cedarwood, and yields an acetate having a similar odour (Bogert
and Slocum, American Perfumer, xviii., 12, G21).
DIMETHYL-HYDROOUINONE.— This body, CcH 4 (OCH 3 ) 2 ,

the dimethyl ether of hydroquinone, is a ciystalline bodj^
meltmg at 5G° and boiling at 205°. It has an odour of the new-
mo^vn haj^ type, and blends well with coumarin in flov^er odour.s,
and is an excellent fixative.

DIMETHYL-OCTENE-OL. — This alcohol re.sults from the
interaction of acetobutanol and ? -butyl magimsium iodide. It
boils at 103° to 108° at 12 mm., and yields an acetate having a
fine floral odour. An isomeric alcohol re.sults from the condensa-
tion of aceto-propanol and f-am 3 d-magnesium iodide. It boils at
107° to 109° at 12 mm., and both it and its acetate have a fine
odour resembling benzoin (Bogert and Slocum, American Perfumer,
etc., xviii., 12, G21).

DIMETHYL-PHLORACETOPHENONE.— The essential
oil of Bhimea halsamifera and several of the xanthox^duni oils
contain a small cpiantity of this ketone, of the formula CcHo
(C0CH3)(0H)(0CH3)(0CH3). It is an odorous crystalline sub-
stance, melting at 82° to 83°.

DIMETHYL-THYMOHYDROOUINONE.— This quinone
ether is a natural constituent of the essential oils of Armica
moniana {Annahn, 170, 3G3) and Eiqmioruim iriplinerve. It is
an odorous oil having a specific gra\dty 0-991 at 20° ; refractive
index, 1-5134 ; and boiling point, 249°.

DINITRO-BUTYL-ot-CRESOL methyl ether.—

This is the “ musk ambrette " of commerce. It melts at 85°.
{Vide “Musk.=’)

DINITRO-BUTYL-/77 -XYLENE.— The acetyl derivative of
this body is ketone musk. It has a rich musk odour, and melts
at 134° to 135°. {Vide “ Musk, Artificial.”)

DINITRO-BUTYL-XYLYL- ALDEHYDE.— This body is
one of the least common artificial musks, known as “ aldeltyde
musk.” It is a crvstalline compound, melting at 112°. {Vide
“ Musk.”)

DINITRO-BUTYL-XYLYL CYANIDE.— This body is a
comparative^ rare artificial musk {vide “ Musk ”). It is a cr^'-stal-
line body, melting at 110°.

DIOSPHENOL. — Diosphenol, or buchu camphor, OioHigOg,
is a phenolic ketone, occurring naturallj’- in certain of the buchu

ISO

PEBFTJ 31 EBY

leaf oils. It is a crystalline substance having the follo^Y^ag
characters : melting point, 84° ; boiling point, 232° ; and optical
rotation, + 0°. It has been artificially prepared by Semmler and
:\Iackenzie {BericJiie, 1906, 39, 1158) by oxidising oxymethylene-
menthone and inverting the resulting diketonc vdth caustic
alkali. Cusuiano {Att. B. Acad. d. Lined, 5, 22, ii., 1913, 569)
has also prepared it artificially by treating dibromo-menthone
with caustic alkali and saturating the resulting liquid with carbon
dioxide. Diosphenol, usually in the form of buchu oil rich in the
ketone, is of value when used in very small amoimt in odom’s
where a suggestion of black currant flowers and fruits has been
introduced. It also gives a characteristic tone to flavouring
essence of black currant. Diosphenol has also been prepared from
piperitone (q.v.).

DIPHENYL-KETONE. — ^This body is generally known as
benzophenone {q.v.).

DIPHENYL-METHANE. — Diphenjd-methane CgHg-CHa
OgHg is a very valuable synthetic perfume. Its odour is very
powerful, and resembles that of geranium leaves, so that, in
common with diphenyl oxide, it shares the name “ artificial
geranium.” It is a hydrocarbon, and therefore very stable in
the presence of free alkali, so that it is of considerable value in
soap perfumery. It is a crystalline compound melting at 26° to
27°, and boiling at 261°. It is prepared by the action of zinc
dust on a mixture of benzyl chloride and benzene, or by the
condensation of benzene with formic aldehyde in the presence
of a small quantity of sulphuric acid.

DIPHENYL OXIDE.— This body CgHg.O.CeHg is a crystal-
line compound which has come into considerable vogue as a
synthetic geranium. Its odour is strongly geranium, with a
suggestion of orange and hyacinth. It forms crystals melting
at 28°, and boiling at 258° to 259°. It was originally prepared
by Gladstone and Tribe by the distillation of phenol-alummium.
It can be prepared by the dry distillation of copper benzoate, or
b3’' digesting diazo-benzene sulphate with phenol. This body is
a good example of the fact that bodies are produced by the
chemist without their odom* values being realised, unless the
chemist happens to be a perfume expert. This body was discovered
in 1899, and the chemist who prepared it reported that “ it has
an indescribable orange-bice odour, but has not found any
practical application.” It was not until about fifteen years later

181

PEBFU MERY

tliat its geranium odour was noticed, and it then raj)idl 3 ’- became
a commercial iiroduct. (See also La Parfumerie Moderne, 1923, 51.)

DIPTERYX ODORATA. — ^Thc highly fragrant seeds known
as Tonkin or Tonka beans are derived from Dipicryx odorata and
DlpteryxoppositifoUa, large trees of the natural order Leguminosui,
natives of Cayenne. The former grows principallj’- in Guiana, and
the latter in Brazil. In British Guiana the tree is known by the
natives as Kuswam. It grows (according to SaAver, “ Odoro-
graphia,” vol. i., p. 132) plentifully in some localities, e.specially
above and on the islands in the rai)ids of the Esc[uibo River. The
beans contain a fixed oil, which, when expressed, contains a
certain amount of the perfume of the bean, and Avhich is highly
esteemed as a hair oil by the native.s. Tliis, it is suggested, ma}^
be the origin of the formerly Avell-known (so-called) hair restorer
known as balm of Columbia. The tree also gi’ows in I\Iartinicjiue.

According to Albes {American- Perfumer, 1916, 10, 278), the best
beans come from the region between the Caura and Cuchivero
rivers, in eastern Venezuela, where the soil seems to be most
favourable for the groAvth of the Tonlca bean tree. The trees are
not usuallj* found in groves, but groAv singly, though small clumps
arc occasionally met Avith. The gathering of the nuts is thus all
the more difficult and arduous. CultiAmtion of the tree has been
attempted in Trinidad and other parts of the West Indies, but
as it takes from ton to tAvelve j'ears for a tree to come into bearing,
this has apparentlj" discouraged the planters, and the Avild product
is still depended upon to supply the markets. The crops seem to
bo A’-cry irregular. As a rule, there does not seem to be more than
one good crop in three 3 ’ears, production in the interval being so
small that it hardily pays to collect the beans.

In Venezuela the tree is knoAvn as sarrap>ia, the men engaged
in the collection of the seeds being called sarrajneros. Ciudad
Bolivar is the centre of the Tonka bean industry.

Birds, especially of the parrot family, frequently cause con-
siderable damage. Thc}* feed on the small immature fruit of the
trees in the months of October and November, long before the
beans are ready to bo gathered. Where these birds have eaten
the ground is strovai A\dth fruit only claAved, and then aAAdcAvardlj"
dropped, or perhaps AA’ith just a small piece bitten off.

About the beginning of February the sarrajoieros begin to
organise their expeditions to the interior to collect the beans.
For tAVO or three months thereafter the Caura River is animated
AA’ith boats of every kind and description, some of them carrying

182

FERFU MEBy

entire families on their w&y to the districts where the trees are
found. As soon as a suitable place has been found, ranchos or
huts are built, which are to be the sarrajneros’ homes for perhaps
two or three months. Once the fruit of the trees in the vicinity
of the ranchos has been gathered, the men go farther into the
forests, sometimes taking their supplies with them and remaining
absent for a week or two.

The fruit of the Tonka bean tree resembles a mango in appear-
ance ; it has but little pulp, wliich is sticky and tasteless, but
edible. The seed (or bean) is covered vdth a hard furrj* substance.
After a sufficient quantity of the fruit has been gathered, it is
taken to some open place, where it is further treated. The hard
shell is carefully crushed between two stones, and the single
oblong seed removed and dried in the sun. These dried seeds are
the Tonlva beans of commerce as they are sold to the merchants
and exporters in Ciudad Bolivar. By the end of May or the
beginning of June the crop is completed.

Before the beans are exported they go through a process of
crystallising by being steeped in strong rum or alcohol. Casks
open at one end are filled vdth the beans to within about a foot
from the top. The rum is then poured in until the cask is full,
when it is covered by layers of gunny bags. After twenty-four
hours the rum not absorbed is rim off, and the beans are spread
out to dry in a exurent of air. When first taken out, the beans are
of dark brovm colour and are swollen with the absorbed fluid. On
drying they shrink and become covered with coumarin crystals.

The tree reaches a height of 60 to 90 feet. The pods each contain
one seed, shaped like an almond, but larger, and covered vdth a
black shiny skin. When the seed is ripe, the seed pod does not
open, as is usual with leguminous plants, but, when detached from
the stem, rapidly acquires a powerful aromatic odour suggestive,
when very dilute, of new-mown hay. This is due to the gradual
development of about 3 per cent, of coumarin {q.v.), which may be
seen in white crystals beneath the skin of the seed and between
the lobes. The comparatively large amount of fixed oil present
in the seed acts as a fixative, and prevents the coumarin from
evaporating more than slowly, so that the beans retain then odour
for a very long period. The beans are often found to be covered
with a crystalline layer of coumarin, wliich is either natxual on
account of age, the coumarin having been gradually volatilised
from the centre to the surface, or, by their having been steeped
in rum and then laid out to dry as above described.

183

PER F U ME R Y

To prepare coumarin from the natural source the finely cut up
material is boiled with 80 per cent, alcohol, the alcoholic solution
filtered and concentrated, and the concentrate is mixed "with four
times its volume of boiling water. The solution is filtered through
wetted filter paper to remove fat and oil, and then set aside to
cool. The coumarin then crystallises out, and may be purified
b}’^ recrystallising after dissolving in hot water and shalcing vith
animal charcoal to decolourise. The so-called “ Angostura " beans
are the larger and more esteemed, the “ Para ” beans being
smaller and of less fine odour. {Vide “ Coumarin,' and ” Liatris
odoratissima.”)

DISTILLATION, FRACTIONAL, IN ANALYSIS.— The
anatysis of essential oils embraces the determination of as many
characters as pos.sible of the oil to be examined. Ob^^.ousl5’■, the
greater the number of characters determined, all of which are
compared with the knovm characters of aiithentic oils, the greater
is the chance of coming to a correct conclusion as to whether the
oil examined is genuine or not. This state of facts, however, is as
well known to the dishonest adulterator as to the honest chemist,
and the former is always endeavouring to keep a step in advance
of the latter in order to confuse and mislead him. Endeavours
are made to make mixtm'es which shall have the same specific
gravity, optical rotation, refractive index, and other general
characters as a pure essential oil has. It is ob^nous, however,
that the greater the number of such characters to be determined,
the less the chance of the adulterator deceiving the analj’st is.
Hence the necessity of multiplying the number of analytical
characters to be determined to the greatest possible extent. This
is most satisfactorily achieved by subjecting the oil to fractional
distillation, and so separating the oil into fractions boiling at
different temperatures, and therefore containing different con-
stituents, and' determining all the usual characters on all the
fractions so obtained. Whilst a skilful adulterator may success-
fully imitate all the usually determined characters of an essential
oil as a whole, it is a practical impossibility, except in very rare
cases, for him to so compound an oil that, when it is sej)arated
into numerous fractions, all the fractions shall have the same
characters as the corresponding fractions of the genuine oil.

In fractionatmg an oil, the character of the oil must be taken
into consideration in determining the method of distillation to be
employed. Many oils can be fractionated by distillation at
ordinary pressure in either an ordinary Wurtz flask or in a three-

184

P ERF U ME By

bulb flask, which- effects a rather better separation. Further
still, heads of various forms may be used, which effect a still better
separation of the various constituents. Other oils must be distilled
under reduced pressure, the pressure varying according to the
nature of the constituents of the oil. But, whatever the conditions
of fractionation, it is- absolutely essential that the}^ should be
identical in the case of the sample under examination and the
standard sample with which it is being compared.

To exemplify the value of this method of examinmg essential
oils, the following examples may be quoted ; —

The VTiter (E. J. P.) and Bennett have examined suspected oils
of peppermint with the following results.

A pure American peppermint oil gave the follovung results, the
fractions being collected in quantities of 12-5 per cent, as distilla-
tion proceeded : —

Fraction.

Specific gravity.

Rotation.

Rofractivo index.

■

0-898

- 10°

1-4660

0-903

— 14°

1-4635

0-907

— 16°

1-4645

0-910

- 20°

• 1-4640

•5

0-912 !

- 23°

1-4615

0:912

1 - 23° ,

1 1-4615

0-915

- 34° I

1 1-4630

0-962

___ j

1-4790

An oil which was suspected, and finallj’- found to be adulterated
vith the artificial ester triacetin, was distilled under identical
conditions, and the fractions examined, vdth the follomng
results : —

Fraction.

Specific gravity.

Rotation.

Refractive index.

— 15°

1-4645

— 15°

1-4670

- 14°

1-4650

— 16°

1-4640

0-926

— 20°

1-4640

0-938

-.22°

1-4640

—

1-4640

1-147

—

1-4450

186

PEB.FV M E B r

Without, discussing the characters of any fractions but tlie last,
it is obvious that the very liigh specific gravity' and the very low
refractive index pointed at once to adiilteration with a high
boiling liquid, of high specific gravity and a refractive index
which, considered with the other characters, indicated the jDresence
• of an aliphatic body. Samples of sandalwood oil which, on the
examination of the oil itself, gave no definite indications of
adulteration, were similarly distilled fractionally. In this case
nine fractions, each of 10 jjer cent., were collected, the remaining
10 per cent, being left as a residue in the distilling flash. A pure
normal sample gave the following values : —

Fraction.

iSiJccific gravity.

Pvotation.

lU'fractive index

0-977

- 18°

1-5078

0-9G4

— IT

1-5038

0-9G9

— 1G°

1-5051

0-975

— 15°

1-50GS

0-979

- 15°

1-5072

0-980

; - 14°

1-5078

0-981 '

1 — 16°

1-50S3

0-981

’ — 18°

‘ 1-5083

1 0-978

— 22°

1-50S6

A suspected sample gave the following results when separated
into identical fractions under identical conditions : —

Fraction.

Spooific gravity.

Potation. I

Pefractivo index.

0-965

- 5° ;

1-503G

0-967

- 5° '

1-5048

0-972

- 4° 30'

1-50G2

0-975

1 — 4° 30' :

1-5075

0-97G

; — 5° 50'

1-5079

0-978

' - G°

1-5083

0-978

: — 8°

1-5080

0-981 .

— 10° 10'

1-5090

0-983

- 14°

1-5095

The great difference in the optical rotation of the fractions
at once reveals the presence of an adulterant. (See also under
" Lavender Oil ” for the fractionation of spike lavender oil.)

ISG

PERFU MEET

This method of examining essential oils is invaluable, and where
there is some abnormality which renders the oil suspicious, but is
not in itself sufficient to condemn it, fractional distillation will
generally decide whether the oil is pure or not.

DISTILLATION OF ESSENTIAL OILS.— The distiUa-
tion of essential oils may be conveniently divided into two sections,
the first invoMng the scientific principles of steam distillation, and
the second dealing with technical considerations, mainly consisting
of the correct ' conditioning of the raAv plant material before
distillation, and its subseq^uent treatment.

- It is first advisable briefly to deal with , the more imijortant
theoretical aspects of the operation of steam distillation considered
apart from the complications wliich arise in the winning of the
oil from its natural source. These theoretical aspects deal with the
phenomena obtaining in the distillation of completely immiscible
liq^uids, in this case water and the essential oil, which, for con-
venience, is considered as a single substance.

The basic law on which the whole science depends is that
enunciated by John Dalton in 1802. Dalton found that, when
two or more gases or vapours which do not associate or react
chemically wfith one another are mixed, each gas exerts the same
pressure as if it alone were present, and that the sum of the
“ partial ” pressures is equal to the total pressure exerted by the
mixture.

It is necessary thoroughly to grasp this conception, and it may
assist if it be stated in another way, viz. : The volume occupied by
a mixture of gases or vapours is equal to the sum of the volumes
which the component gases or vapours would occupy at the same
temperature and pressure.

The saturated — i.e., not superheated — ^vapom’s of liquids which
are completely immiscible with one another foUow Dalton’s law,
the vapoxu’ pressure of the mixture being the sum of the vapour
pressures of the constituents of the mixture, and it is important
to note that the total pressure is not influenced by the relative
amounts of the constituents, i.e., water and essential oil.

If a mixture of immiscible liquids be distilled, the temperature
at wlficli boiling takes place, in the absence of superheating, is
that at which the sum of the vapour pressures is equal to the
external pressure on the system {e.g., the atmospheric pressure).
Bach liquid, considered separately, is consequently boiling at a
lower temperature than it would in the absence of the other
liquid, and this temperature is the same for all the constituents.

187

PEnFU MER Y

The vapour coming from such a boiling mixture contains all the
constituents in proportion by volume to the relative vapour
pressiu’e of each, and the distillate contains all the volatile
ingredients of the original mixture.

Steam DisiUlaiion at Ordinary Pressure. — If and P,, are the

vapour pressures of two immiscible liquids A and B at i ° —
c.g., water and essential oil — the two substances will distil over
p

in the proportion ^ by volume of vapour. If D„ and are the

respective vapour densities at the boiling point of the mixture,
the relative quantities b,y weight W„ and will be expressed
by :

W P D
Wt p,d;

The molecular weight of a substance is equivalent to twice its
vapour density, i.e., M = 2D ; hence we can VTite the equation :

W„ _ P„M„ .

W, - P,M„ ’

vliencc it follows that the mixed vapour will consist of ;

‘ P„ + P„

If we consider 1 litre of the mixed vapour, this will contain
1 litre of the vapour of each component — according to Dalton’s
law — at its particular partial pressure, and the weight of each of
these will be respectively :

0-0896 X M X 273 X P
2 X 760(273 + /.)

Prom this we can calculate, with sufficient accuracy for our
purpose, the amount of water that is necessary to steam-distil
over a given quantit,y of a substance. Thus in the case of benz-
aldeh 3 ’-de, wliieh is the chief constituent of oil of bitter almonds,
its molecular weight is 106, its vapour pressure at 100° C. is
61 mm. ; consequent^ the partial j)ressures of water and benz-
aldeh 3 ’-de at atmospheric pressure and 100° are given b 3 >' :

760 X 760

P'„ X 760

P'„ + P', 760 + 61

= 703-5 for water

P'i, X 760

P'a + 'P'b

61 X 760
760 d- 6i

56-5 for benzaldeh 3 '‘dc,

188

and

PERFU MEli T

the two partial pressures, 703-5 and o6-o, totalling to the atmo-
spheric pressure, 760. Siibstituting in the second equation quoted,
we get :

W„ _ __ 18 X 703-5 _ 68

Wi MftPf, ~ 106 X 56-5 “ 32’

that is, the distillate will consist of 32 per cent, of benzaldeh 3 ’'de
and 68 per cent, of water.

The statements made above refer to steam distillation carried ,
out under ordinary atmospheric pressure. Other pressures,
either greater or less, may be emplo 3 >-ed, as also ma 3 ’^ be super-
heated steam ; further, the oil itself may be superheated, pro-
vided it is not deleteriousl 3 ’- affected b 3 '^ such treatment. Generall 3 ^
the ejffect of increasing the temperature or the pressure is to
increase the proportion of essential oil relatively to the water ;
hence, these alternatives may be usefuUy employed Avhen dealing
with stable bodies, but they are quite unsuited to the more
delicate essential oils, especially those containing esters or
aldehydes in any considerable proportion. For such, the use of
diminished pressure and low temperature is advisable, provided
the duration of the distillation be not thereby undul 3 '^ prolonged.

Distillation ivith Superheated Steam. — ^We vdll first consider the
effect of increasing the temperature of the ingoing steam. If
water be boiled in a boiler, the temperature of the steam varies
with the pressm-e, and if the steam thus generated be allowed to
issue from the boiler into a still worked at some pressure below
that of the boiler {e.g., atmospheric), the temperature of the
steam drops ovdng to the work done in expanding. The table on
p. 190 indicates this drop in temperature in passing from the
given boiler pressures to atmospheric or one-tenth atmospheric
pressure.

The di'op in temperature ma 3 '^ be calculated b 3 ’^ means of
Zeuner’s equation :

pv = BT — Cp”,

where B, C and n are constants, and ^=38-11; ■» = 0-25 ;

p = the pressm'e in atmospheres ; v = the volume in cubic
metres per kilogram ; T = temperature in degrees centigrade.

If the steam in a boiler at temperature T^, absolute pressure p^,
and volume be released into a still at Tg, p^, v^, respectively,
then

= BTj - Cpi" BTg - Cpa”,

189

P E P F U M FRY

whence

Ti - T. = i (j.,- - p,»).

Thus, if a boiler gauge register oC lb. per square inch, coiTespond-
ing to 5 atmospheres absolute pressure, and the steam be injected
into a still at normal atmospheric pressure, from the above table
we find ;

152-2 — To = 38-11 (6°-= —
whence To = 133° C.

Similarl}’-, if 2h — one-tenth of an atmosphere, then To = 116° C.
Thus the temperature of the steam drops from 152° to 133° or

Boiler pre'^sure, i
lb. per pq. incli.^

Initial

tempcratuie.

Temperature af

one atmosphere.

ter expansion to

one-tenth atmo-
spliere.

0 :

100° c.

83-3° C.

111-7

108-1

91-4

14 '

120-0

113-4

96-7

133-9

121-9

105-2

144-0

128-2

111-5

152-2

133-3

116-6

159-2

137-7

121-0

84 1

105-3

141-4

124-7

98 ;

170-8

144-8 !

128-1

112 !

175-8

147-9 !

131-2

126 i

180-3

150-7 i

133-9

Thip is tlie reading on the boiler pressure gauge, and docs not include the
14 lb. duo to the atmosphere.

116 when injected into ci still under atmospheric j^i'^ssure or
one-tenth of atmospheric presstire respectively. In spite, of this
drop in temperature, the steam contains more heat than it would
if it had been generated under ordinaiy pressure — for instance,
by boiling water in the still itself. In this latter instance, the
temperature would be 100° C. instead of 133° ; hence the steam is
said to be superheated or unsaturated. Steam may also be
superheated by passing it through pipes heated by an external
source of heat, and a much greater degree of superheat may be
obtained in this mamier, both these devices merely serve the
purpose of enabling the steam to transfer more heat than it

190

PERFU 3I-E R Y

otherwise would. The use of superheated steam has another
advantage, that there is less condensation due to radiation,
the superheat of the steam causing any condensed water to
evaporate ; so long as liquid water exists in the still, the advantage
of the superheating is lost. If all condensation of steam is pre-
vented, the higher temperature of the superheated steam tends
to increase the proportion of oil in the distiUate ; the same effect
may be obtained by heating the oil to a temperature above that
of the ingoing steam. •

■ Steam Distillation under Increased Pressure. — ^As an alternative
to either of these methods, we may conduct the distillation under
pressures higher than atmospheric. This is done by interposing
a weight or spring loaded valve between the still head and the
condenser ; the method is not, however, in common use.

The effect of the pressure in the still is reflected in the folloAving
figures obtaining for benzaldehyde :

Pressure.

Temperature.

Benzaldehyde.

- 5 ^ atmosphere

45-3° C.

22-5 per cent.

1 s

97*9

31-4 „

140-7

38-2 „

It will be seen that, whereas the proportion of benzaldehyde is
increased, the increase in the temperature to which it is sub-
mitted is very considerable ; this for many substances is
prohibitive.

Steam Distillation under Diminished Pressure. — In order to
reduce the temperature of the distillation, diminished pressure
may be resorted to, this, as is indicated in the table above, also
results in the percentage of the less volatile constituent, e.g., ben-
zaldehyde, being diminished ; there is a further drawback,
inasmuch as there is considerable difficulty in condensing the
vapours produced. For essential oils of a delicate nature, e.g.,
lavender, neroli, the method is to be recommended, but in view
of the technical difficulties involved, it is not usual to resort to
pressmes below one-tenth of an atmosphere.

Steam distillation -with superheated steam under diminished
pressure also offers advantages. •

The Heat of Distillation. — ^The amount of heat-^and hence fuel —
necessary for the steam distillation of a given quantity of an
essential oil can be roughly calculated, but it is necessary to know

191

P E B F U M E R Y

the ainountj the vapour pressure at 100° 0., and the molecular
weight of each constituent of the essential oil. The amount of
steam necessary for each constitixent has first to he ascertained ;
this can he calculated from the molecular weight of the substance
and its vapour pressure at 100° C., as has already been shown.

From the figures thus obtained, the amount of heat necessaiy
to vaporise each ingredient, including the water, can be found,
tlie total heat being the sum of all these. The heat of vaporisation,
H, may be calculated from the change of vapour pressure with
change of temperature, using the formula :

(?P 1-985 T2

Jtl ==: — ^ *

(IT P ’

where T is the absolute temperatiu’o at ijressure P, and dP tlic
small rise in pressure caused by the small rise in temperature dT.

Thus, in the case of C 3 mieme, which has a boiling point of
174° C. — i.e., (174 + 273)° absolute — at the normal pressure of
7G0 mm. : for ever}^ 1 mm. increase in fZP, there is an increase of
0-057° in dT, and the heat of vaporisation at atmospheric pressure
is given b^"

H =

0-057

1-985(174 + 273)
TOO

9156

calories per molecule.

Experimentally, the value has been fomid to be about 2 per
cent, lower, i.e., 8978 calories per molecule. dividing this

value b}’- the molecular weight of cjmiene (134), the heat of
vaporisation for 1 kg. is given as 68.

The following data have been published concerning the heat
of vaporisation of bodies vdiich occur in essential oils : —

Heat of vaporisation.

_ .

Substance.

Temperature.

One kilogram.

One kilogram
molecule.

Acetophenone .

203-7° C.

77-2

9-3 X 103

Anethole .

—

71-5

10-6 „

Benzaldelyde .

—

86-6

9-2 „

Cymene .

175

67-0

9-0 „

Carvacrol

—

68-1 .

10-2 .,

Turpentine

159

69-0

9-4 „

Water

100

536

9-6 „

192

PERFUMERY

Dry Distillation . — few essential oils can be diy distilled,
i.e., without water or steam, at ordinary pressure without under-
going serious decomposition, on accoxmt of the high temperature
that it is necessary to employ. In order to avoid this high tem-
peratm'e, resort may be had to the use of diminished pressure, or
as it is commonly termed, a vacuum.

The problem now involves a consideration of the distillation of
liquids miscible in all proportions. Only the simplest case vdll be
dealt with here, namel}^, that of a mixture of two liquids which
do not associate or react with one another and wliich, in conse-
quence, foUow Dalton’s law.

If Ya and be the vapour pressures of two such liquids A and
B, and these be mixed in the proportion of one molecule of A to
n molecules of B, then the partial pressures and of the two
substances are such that :

• and P,, =

1 l+n

The total vapour pressure P of the mixture is given by ;
100P=:M,P, + (160-M,)P„
where is the molecular weight of A.

By means of this formula it is possible to calculate the vapour
pressures of mixtures of two substances at any pressure. Quite
accurate results are obtained, except in the case of liquids which
associate with one another ; these are, however, apparently of
rare occurrence in essential oils.

Wlien a mixture of two non-associating, miscible liquids is
heated to boiling, the vapour which arises is richer in the more
volatile component than is the liquid ; hence, as distillation pro-
ceeds, the proportion of the less volatile component increases in
the liquid until all of the more volatile has been removed. (The
rnore volatile component is, of course, that having the lower
boiling point.) It follows that the vapour has a higher proportion
of the more volatile component, and if this vapour be con-
densed and subrmtted to a fresh distillation, a further separation
of the mixture into its two components is similarly effected ; by
repeating this series of operations a sufficiently large number of
times, a more or less complete separation may be effected, and tliis,
in effect, is the action of a fractionating column.

Fractionating columns are only resorted to in the case of
essential oils, when it is desired to isolate some particular con-
stituent or to remove midesired bodies, and it must be borne in
mind that the repeated boihng and condensing, upon wliich the
p. 193

PEBFUMER Y

action of sucli columns depend, tend deleteriously to affect the
oils.

The ” Winning ” of Essential Oils . — The considerations set out
in the preceding sections concern the oil after it has been released
from the plant in u'hich it occurs in the natural state. When the
oil has to be distilled out of the plant, a further factor is involved,
namely, the rate at which the plant parts with its essential oil.
This rate may bo so slow that the other factors, such as vapour
pressure, are swamped complete^, and it is therefore of prime
importance to reduce as far as possible the “ lag ” thus occasioned.
In order to accomplish this, it is necessary to submit the plant to
some suitable breaking-up process, but in some instances, such
as geranium, lavender, rosemaiy, the lag is so small that it can
be neglected and no preliminary treatment given to the plant.
The treatment varies vith the nature of the material ; thus berries
may be crushed, seeds and roots ground, w^ood chipped, twigs and
branches cut, and so on. When submitting the raw material to
any preliminaiy treatment, it is well to bear in mind that exposure
to heat and air tends to cause loss of oil through evaporation and
oxidation.

Two methods of distillation are videty practised, namely,
distillation by boiling with water (water distillation), and dis-
tillation bj^ the injection of steam (steam distillation). The former
is employed on account of its convenience and the simplicity of
the necessary apparatus, but the latter, v'hich in general gives
the better product, is employed in the larger distilleries almost
exclusively.

The apparatus may be constructed of almost any convenient
metal, copper being usually preferred ; w'ood is also often employed
for the still body. The precise shape and size of the still is not of
great impoidance ; cylindrical stills are the most common. The
material to be distilled is usually supported on a perforated false
bottom, in order to keep it from direct contact vith the hot
bottom or steam coils, as the case may be, such contact tending
to cause destructive distillation, with the consequent production
of evil smelling-bodies. Instead of a perforated false bottom a
gauge basket is sometimes employed, the spent charge being
removed by lifting the basket out of the still after taking off the
cover.

The vapours coming from the stiU are condensed by passage
through a spiral coil immersed in a tank of running cold water,
or by means of special condensers, such as the “ Ideal,” in wliich

104

PEBFVMEBl

the vapour is caused to pass between narrow annular spaces
formed by fixing, conccntricall}^ one tube inside another of
slight!}’ larger diameter, a wire being wound spirall}' in the space
between tlie two tubes.

The liquid issuing from the condenser consists of a mixture of
oil and water ; usually the oil is lighter than water, aiid in course
of time floats out — ocfcasionally, however, it or some fraction of it
is heavier and sinks ; the two la3'ers are sciiaratcd automatically
by means of “ essenciers,’’ which consist of vessels having overflow
tubes arranged at suitable heights. In the case of some oils,
considerable difficulty is experienced in obtaining a good separa-
tion of oil and Avater owing to emulsification, the Avater remaining
cloud}’, even after standing many hours. There are three common
methods for dealing AA’ith this difficulty : (1) retm-ning the cloudy
AA'ater to the stiU instead of suppl}’ing fresh Avater or steam
(cohobation) ; (2) extracting the Avater Avith an immiscible

solvent, such as benzene ; (3) passing the AA'ater through some
material AAdiich Avill absorb the oil, such as kiesolguhr or saAvdust,
and then subsequently steam distilling the mass.

When the oil has eventually been separated from the mass of
the Avatcr, it should be dried by filtering or by setting aside in a
cool place until clear, placed in Avell-closcd, suitable packages,
e.g., bottles, tinned copper or tinned iron containers, and stored in
a cool place ; careless treatment of the oil may result in rancidity,
lack of sAA’eetncss, or bad colour. T. H. D.

DISTILLED WATERS. — A certain number of essential oils
contain sufficient highly aromatic constituents which are soluble
in Avater to such an extent that they impart to the distillation
AA’ater an odour which makes the Avater sufficiently aromatic to
be of considerable value to the perfumer. In general, hoAvever,
the situation of the distillery and the conditions of the distillation,
coupled AAith economic considerations, such as the disproportionate
freights for the conveyance of a comparatively cheap article, are
such as to make the trade in such aromatic Avaters either impossible
or unremunerative. It is, of course, only a feAv oils Avhich yield
distillation waters of any value. Where the process is possible,
distillation waters Avhich contain dissolved essential oil, and which
are not saleable as such, are, as far as possible, returned to the
still so that a further loss of oil, which would take place if fresh
Avater Avere used, is thus avoided. The principal distilled waters
which form commercial articles are rose water and orange flower
water. Such waters are usually sold under a conventional name

195 13-2

PEBFU MEET

as to concentration, such as aqua rosas triplex.” Such terms
are more or less arbitrary, as they do not indicate that, for example,
3 lb. of flowers have been distilled for 1 lb. of the water, but that,
for example, it is an early fraction of the distillation water, so
that considerable dilution has not taken place. It is obvious that
the distillation water and the essential oil itself will not have
identical odours, as their odour is not due to identical constituents.
For example, phenyl-ethyl alcohol is a regular constituent of the
rose flower. This alcohol is comparatively soluble in water, so
that it is substantially absent from otto of rose (the essential oil
of the rose), whilst it is responsible tor the characteristic odour of
rose water. Apart from the two waters mentioned above and a
very few others, such as cherry laurel, the bullc of so-caUed
aromatic waters are made by dissolving a very small amount of
essential oil in a little alcohol and pouring this into a large volume
of water, which is weU agitated and eventually filtered, if necessary,
with the aid of filtering powder. (See also “ Rose Water ” and
“ Orange Flower Water.”)

Gujmt {Jour, de Plmrm. et de CJiivi., vii., 1916, 13, 37) has
investigated the cause of the green discoloration which often
takes place in perfumed and medicinal waters. The follovdng are,
according to Schimmel c& Co. {Report, 1916, 39), Guyot’s con-
clusions : —

“ The coloration is due to an aerobic microbe forming colomiess
clusters of rod-hke organisms, 4 to 5 p. long and 0-5 p. wide, which
are colomed by basic aniline dyes and methyl blue, and assume
the Ziehl and Gram colorations. This microbe is different from
Bacilhis liquefaciens fluorescens and from most water bacteria
producing green fluorescence. It produces a green non-fiuorescent
coloration. It also differs from Bacillus pyocyaneus as well as
from Lesage’s baciUus. The new microbe appears to be able to
exist vdthout giving off the green coloiu’ ; its colour -forming
properties are dependent upon extraneous surroundings and the
composition of its cultivating solution. Oxidising media and
oxygen favour the development of the green coloration, while
reducing substances weaken it and make it disappear entirely.
Light has a favourable influence on the development of the green
colour. Zinc acts as a reducing substance ; this is the reason why
green coloration does not take place with orange flower water
stored in zuic vessels. An alkaline reaction of the Hquid favours
the development of the microbe.

“ The green colom’mg matter evidently belongs to the group of

196

P ERF V MERY

aurantiaclilorines ; it is insoluble in alcoliol, methyl alcohol, ether,
chloroform, and benzene, but dissolves in water. To isolate the
colour, undyed wool is immersed in the liquid when the colour is
precipitated on tlie wool. If the wool is treated with diluted acids,
the green colour is converted into a brick-red one, soluble in
alcohol, methyl alcohol, ether, chloroform, and benzene. If this
solution is neutralised, the red colour is once again converted into
the crecn colour, soluble in water. Cherr3'’ laurel water never
shows green coloration. No decrease in odour is noticeable in
the waters owing to the change involved by the green coloration ;
on the contrary, with orange flower water, for instance, the
opposite effect maj’’ be observed.”

Juillet {Rourc-Bcrlraml Fils, Bvlhtin, October, 1013, 22) has
carried out an investigation on the methods of preserving distilled
waters and preparing them in a sterile condition. The follovdng
is an outline of his historical resume of tlie question : —

These waters are exceedingly unstable preparations ; their
alterations are sometimes of a physico-chemical order (evaporation
of certain active principles, oxidation of essential oils, etc.), some-
times of a biological nature (attacks by fungi or algse). Conse-
quentl 3 ^ the question of their preservation has for a long time
occupied the attention of pharmacologists, and, wdiile not pre-
suming to recapitulate here all the history of the problem, it
seems to me of interest to mention its main outlines.

At the beginning of the last centmy there was at first a belief
(Bahoff and De 3 'cux) in the transformation of the essential oil
into mucilage, a fact which appeared to be demonstrated to the
authors by the observation of the presence of “ mucilage ” in the
watery extracts obtained artificially by dissolving an essential oil
in water.

Soubeiran was the first to recognise the organised structure of
these supposed mucilages, wliich Biasoletto shortl 3 ’' afterwards.
(1832) classified among the algaj of the germs’ Hygrocrocis. Later,
L. Marchand (1878 and 1883) and other observers showed that
these Hygrooroois are fungi, the abnormal forms of which are the
result of the special conditions of existence to which they are
subject in the watery extracts. The study of these micro-
organisms was the subject of investigations carried out by Tulasne,
de Barry, Thuret, Bornet, and van Tieghem ; and in 1896
Barnouvin, returning to the question, classified them in order of
importance among the fungi, the bacteria and the algfe.

The fungi, by far the most frequent, had first been classed in

197

PERFXJ MERY

^ the genus Hygrocrocis ; but it is well recognised at the present
day that the latter reallj’' comprises different genera, the characters
of which are profoundly modified by the composition of the media
in which the plants live. The most abundant and the most
frequent is Penicillmm glancum, then come Aspergillus and
Sterigmatocyslis sioecies ; the group of the Demaiia is also very
largelj’^ reinesented by various species of Gladosporium, Dematium,
AUernaria, to which must be added Gephalosphermm, Fusarmm,
Mucor, etc. Man}’- of these fungi may occur under these con-
ditions as yeast-lilce forms, and even may only affect this form in
certain watery extracts.

The bacteria are, as a rule, of the genera Leptotlirix, Micrococcus
and Bacillus, with numerous chromogenic species {B. auraniii,
B. fluorescens) capable of communicating to the distilled waters
in which they grow the coloiu' of their pigments.

The algas are unicellular, and belong to the genera Protococcus,
Hemaiococcus and Goccocliloris.

These various organisms may, moreover, coexist in one and the
same water. But, whether they are alone or associated, they
ahvays provoke profound modifications in the distilled waters
infected by them.

The changes of a physico-chemical order necessarily vary with
the natm-e of the active principle predominant in the water.
Thus cherry laurel water may lose by evaporation a portion of
its hych'ocyanic acid, whilst by oxidation its essential oil may be
converted into benzoic acid ; under the same influence the
essential oil dissolved in orange flower water is converted into
acetic acid, and cinnamic acid is constantly present in cinnamon
water.

Numerous attempts have been made to remedy these incon-
veniences, and proposals have been made, one after another, for
filtration, chilling, heating, sterilisation by Appert’s method,
IDreservation in full bottles, well corked and in cool dark places,
the addition, often unsatisfactory, of alcohol, etc., means more or
less palliative, the effects of which are often contradictory and
always insufficient.

Juillet describes in detail the best method of sterilising the
stills used, and shows that filtration through Chamberland filters
is of extreme value in rendering these waters sterile, and, if they
are kept under suitable conditions after having been sterilised,
they will remain unchanged for a considerable time. For details,
the original paper should be consulted.

198

PERFU M EE Y

DITTANY OIL. — ^Tlie herb Ciinila origcincides, one of the
North American Lahiatcc, jnelds 0-7 per cent, of a reddish-bro'mi
oil resembling thj-me in odour. It has a .specific gra^fity 0-91.5, and
contains about 40 per cent, of phenols, probably mostty tlijunol.

DJAhlBOL LEAF OIL. — ^The leaves of Psidiuni Guajava,
one of the Myrtacen:, a tree indigenous to tropical America, yield
about 0-36 per cent, of essential oil of specific gra-vity about 1-069,
and boiling at 237°. Scliiminel cO Co. have distilled some leaves
from Santiago do Cuba, and obtained 0-2 per cent, of an aromatic
oil hamng tlie following characters : —

Specific gravity .... 0-9157

Optical rotation . . . . — 10 ° 5 '

Refractive index .... 1-4964

Acid value . . . . .2

Ester value . . . . . 6-4

DOREMA AMMONIACUiM.— See “ Ammoniacum.”

DOREMONE. — This body is a ketone of the formula
Ci 5 H 2 cO> occurring in the essential oil of ammoniacum. It has
a specific gravity 0-8765 at 20° ; optical rotation, -{- 3° 30' ;
refractive index, 1-4716 ; and boiling point about 150° at 12 mm.
On reduction with sodium and alcohol it j-ields the corresponding
alcohol, doremol C 15 H 27 OH, which has the following characters :
specific gravity, 0-870 ; optical rotation, + 3° ; refractive index,
1-4713 ; and boiling point, 145° to 150° at 12 mm. It is present
in the oil in the form of its acetic ester. The ketone, alcohol and
ester are all odorous liquids.

DORYPHORA SASSAFRAS, OIL OF. — The leaves of
Dorypliora sassafras have been found by Penfold {Jour, and Proc.
Royal Soc. N.S.W., Iv., 270) to jdeld up to 0-85 per cent, of essential
oil of a deep yellow or brovm colour, with a marked odour of
safrol. Two samples were examined, one from leaves gathered
at hlonga, the other from Currowan. They had the characters
given in the table on p. 200 .

DOUGLAS FIR OIL. — ^This oil requires a good deal of
further examination. The reports made by Brandel and Sweet
and by Schorger on oils stated to be derived from the leaves of
the Douglas pine, and botanicaUy described as Pseicdoisiiga
taxifolia, indicate an oil of no particular perfume value. Schorger
gives the following as the approximate composition of the oil :
a-pinene, 25 per cent. ; /?-pinene, 48 per cent. ; dipentene and
limonene, 6 per cent. ; furfural, traces ; esters, 6-1 per cent. ;

199

PERFUMER 7

free borneol, G-5 per cent ; and a green oil of unknown
constitution, 3 per cent.

According to Henry and Flood {Proc. Roy. Irish Acad., Ma 3 ’',
1920) this tree is Pseudotsziga glauca, whilst the Oregon Douglas
fir is the true Pseudotsuga taxifolia. These authors give the
details of tlie examination of the oils distilled from the leaves of
both trees grown in England, by C. T. Bennet, who reports as
follows upon them. The oil from the leaves of the Oregon Douglas
fir was distilled from 50 lb. of the leaves from trees growing at
Buckhold, Berks. The jdeld was 0*11 per cent., and the oil had
the following eharacters : specific gravity, 0-87G ; optical rotation,
— 7° ; refractive index, 1*4835 ; and ester content, 12*4 per cent.
He stated that the ester value was 'much lower than that of the

IMonga.

Currowan.

Specific gravity

1*021-1*031

0*981

Optical rotation

-{- 16° to + 22°

+ 28°

Refractive index

1*5058-1*5091

1*4898

Ester number

Safrol ....

G0-G5 per cent.

30 per cent.

Camphor

10-15

Pinene .

Sesquiterpene .

—

Eugenol

3*5 „

Eugenol methyl ether

Present.

Colorado Douglas fir oil, but that the odour was much more
fragrant. The oil contains dipentene or limonene, but no, or onl.y
traces of, pinene. An api^reciable quantitj’- of geraniol was
separated on fractionation, and it is to this that the aromatic
odour appears prineqjally to be due. By acetjdation 31*5 per eent.
of alcohols was indicated. Born 3 d acetate somewhat masks the
geraniol odour of the oil. Citral is present in traces. The oil from
the Colorado Douglas fir was distilled from leaves from trees
grovm in East Liss, Hampshire. The 3 deld was 0*31 per cent, of
an oil having the following characters : specific gravity, 0*905 ;
optical rotation, — 4G° ; refractive index, 1*4717 ; and esters,
as born 3 d acetate, 34*5 per cent. The terpenes present consist
mainly of pinene. The odour is due principally to the bornyl
acetate present. (See also “ Pine Needle Oils.”)

DRYOBALANOPS AROMATIGA, OIL OF.— The so-
called Borneo camphor tree is a native of Sumatra and north-west

200

PERFUMEEl

Borneo. Camphor as first kno'mi in this country (Arabic Kafur,
Sanscrit Kajntm = a pure white substance) was brought from
the land kno'rnr as Kaisur, the present Sumatra, and was the
product of Dryohalanops Camphora, a splendid forest tree growing
in abundance in Borneo and on the west and north-west coasts
of Sumatra. This substance, however, is now known to be borncol,
and not true camphor. According to Sawer (“ Odorographia,”
vol. i., p. 334), the borneol can only be obtained b}’’ the destruction
of the trees, all of which do not contain borneol. IMany of them
only contain an essential oil which has not yet developed any
borneol. Practicallj’ all the borneol obtained from these trees is
used locally or exported to China, either for incense or embalming
purposes. Several of the Russian june needle oils are so rich in
borneol or its esters that competition with such oils is out of the
fjucstion. The essential oil has a specific gravity 0*918 ; optical
rotation, + 11° ; and refractive index, 1*4885. Oils of low
specific gravity have been deprived of borneol. -

DUODEGYL ALCOHOL. — This body has the formula
CH 3 (CH 2 )io CHoOH, and is used in minute proportions in rounding
off floral odours. It is a liquid boiling at 257°, crystallising at low
temperatures, and melting at 14°. It is also knovTi as lauric
alcohol. Its specific gravity is 0*831 at 24°.

DUODEGYL ALDEHYDE. — See under “ Aldehydes, Higher
Fatty.”

EAU DE COLOGNE.— EAU DE COLOGNE is one of the
most popular toilet perfumes — probablj- the most popular — in the
world. It is not, of course, intended to give formuloe for any
perfume in this work, but the general characters of this almost
universally used water may be indicated. The original eau de
Cologne was in all probability actually invented in the towm of
Cologne b}’- one Jean-Marie Farina, who was born at Sainte jMarie
jMajeure, in Italy, and went to Cologne to trade in perfumes, and
invented this famous blend in 1709. Another version of its
original manufacture is that it was first placed on the market by
one Paul de Feminis in Milan, and was afterwards made in
'Cologne from 1690. The secret was then passed on to his
nephew, Jean-Antoine Farina, who started manufacturing it in
Paris. IVhichever version is correct, there is no doubt that from
-the commencement of the eighteenth century eau de Cologne has
been a very popular perfume, and many rival manufacturers, both
in Cologne and elsewhere, have carried on its manufacture. The

201

PERFU MJSB. Y

trade name “ Farina ” proved somewhat of a stumbling-block
to rivals to the original maker, but they found it easy to import
members of the Farina family to Cologne, and so became entitled
to use the name. Endless lawsuits have taken place in regard to
the matter, and it is not very easy to say whether any maker
to-day uses the original recipe. Le ]\Iaout satirically wrote the
follovdng quatrain on the “ Farina ” position in Cologne

Ils etaient deux alors : ils sont mille ajourd’ hui
Sur ses temps primitifs le doux progi'es a lui,

Et cliaque jour le Eliin vers Cologne charrie
De nombreiix Farinas, tous ‘ seal,’ tous Jean-Marie.

Eau de Cologne is in substance the product of Italian essential
oils, mixed with one or two others, which certainly are not
German. It is so delicate a perfume that only the finest alcohol
should be used for its preparation— so much so, that this fact has
given rise to the name “Cologne sp)irit,” which indicates the
liighest grade of alcohol for perfumery purposes. The finest Eau
de Cologne is that produced, not by the mere mixing of the
ingredients, but hy distilling the alcohol with most of the ingre-
dients, and adding certain ingredients after the distillation. The
longer the perfume is allowed to mature — up to one year — the
better it vill be. Hundreds of formulse have been pubfished for
this perfume, but the follovdng is sufficient to indicate its general
characters. The bulk of the ingredients, in which bergamot oil
should prevail, and which include lemon and orange oils, with a
httle lavender oil and orris root, are macerated vdth alcohol for
several days, and then carefully distfiled without the apphcation
of naked heat. To the distillate neroli oil, a very small amount
of rosemary oil, and a trace of a fixative such as benzoin, are
then added, and the whole allowed to mature for as long as
possible. Where a cheaper eau de Cologne is desu’ed, the oils are
merely mixed Avith the alcohol, without distillation, often in the
form of terpeneless oils. Numerous formulae, which as a rule
are merely indicative, as obviously valuable trade secrets rarelv
leak out, will be found m any of the text-books of practical
perfume making.

EGLANTINE. — This well kno^vn “ fancy ” p)6rfume is in-
variably based on one or other (or mixtures) of the three esters —
methyl phenylacetate, butyl (or isobutyl) phenylacetate, and
isobutyl benzoate.

ELECAMPANE OIL. — ^The root of Inula Helenium, a plant
of the natural order Comjoositce, yields from 1 to 3 per cent, of a

202

PERFUMERY

semi-solid essential oil, having an odour vliich recalls that of
ladanuin. This oil liquefies at from 30° to 45°, and has a specific
gravity, 1-015 to 1-03S at 30° (melted) ; optical rotation, + 123°
45' ; refractive index, 1-5221 ; acid value, 6 to S ; ester value,
160 to ISO ; and ester value after acetylation, 199. The oil
consists almost entirely of an anhydride, named alantolactone,
^'15^20 02> ^^so known as helinin. This is a crystalline compomad,
melting at 76°, and boiling at 275°.

ELEMI. — See “ Canarium Eesins.’'

ELEMOL. — ^This substance is a crj’stalline sesquiterpene
alcohol, isolated from the essential oil of Manila elemi, by Schimmel
cb Go. It is the principal ingi-edient of elemi oil, to which it owes
its fixative properties.

Jarnsch and Fautl {BericJile, 1923, 56, 1363) have shown that
clemol is a bicyclic sespuiterpene alcohol, which is isomerised to a
liquid alcohol by benzo5dation. They term the crystalline body
a-elemol and the liquid body /9-elemol. Pure a-elemol CisHogO
forms fine needles melting at 46°, and boiling at 142° to 143°" at

10 mm. /5-eIemol has a specific gravity 0-9419 at 18° ; refractive
index, 1-5070 at 18° ; and boiling point, 143° to 144° at 10 mm.

ERIOSTEMON CROWEI, OIL OF.— According to Pen-
fold and Morrison {Jour, and Proc. Roy. Soc. N.S.W., Ivi., 227)
the leaves and terminal branchlets of this plant (previously
described as Crowea salnjna) yield about 0-4 per cent, of essential

011 having a safrol-like odour. The oil has the foUov-ing
characters : —

Specific gravity . . . 1-109-1-124

Optical rotation . . . + 0°

Refractive index . . . 1-5302-1-5321

The oil contains a little pinene, but contains about 90 per cent,
of a phenol ether, which has been named croweacin. Two pre-
parations had the following characters : —

Boiling point at 10 mm. .

130-131°

130-132°

Boiling point at 766 mm.

—

256-258°

Specific gravity

1-1339

(uncorrected)

1-1298

Optical rotation

+ 0°

4-0°

Refractive index at 20° .

1-5330

-1-5328

Its formula appears to be C11H12O3.

203

PERFUMERY

ERYNGIUM CAMPESTRE, OIL OF.— The essential oil
of Eryngium campesire, an umbelliferous plant’ growing in the
South of France, is a pleasant smelling liquid, somewhat reminding
one of oil of musk seed. It has {SchiinmeV s Report, October, 1905 ,
73 ) the foUo'v^dng characters : —

Specific gravity .... 0’904

Optical rotation . . . . — 5 ° 42 '

Refractive index . . 1*4852

Ester value ..... 10*5

ESTERS.- — ^The esters, as a class, are amongst the most
important of the odorous constituents of essential oils. An ester
is a combination of an alcohol "with an acid, the combination being
brought about by the elimination of water. For example, ethyl
alcohol and acetic acid combine in accordance with the follovdng
equation, •^'liich is typical : —

C2H5OH + HOOC.CH3 = C2H5OOC.CH3 + H2O.

Ethyl alcohol Acetic acid Ethyl acetate AVatcr

If the alcohol be dihydric, two molecules of acid will react
with one of the alcohol, or if the acid be dibasic, then two molecules
of the alcohol •wfil react •with one of the acid, and so on. Thus,
glycerine bemg a triliydi'ic alcohol, 03115(011)3 can combine with
three molecules of acetic acid, formmg the triacetic ester, triace-
tin 03115(0.000113)3. Or, again, succinie acid, being dibasic,
02H4(000H)2 forms diethyl succmate, 03114.(000.02115)2, with
two molecules of ethyl alcohol.

Esters are prepared by the interaction of the alcohols and acids
at an elevated temperature, the reaction frequently being assisted
by the presence of such bodies as anhydrous sodium acetate,
which either acts as a catalyst or as a dehydrating agent. The
reaction is, however, more complete if the acid anhydride is
employed instead of the acid itself. Thus :

2 R.OH -k O(OOR') = 2R.O.OOR' + HgO,
where R is the radicle of the alcohol and R' that of the acid.
For other methods of formation, such as the use of acid chlorides,
ordinary text-books on organic chemistry should be consulted.

Many essential oils contain considerable quantities of esters.
For example, oils of wintergreen and sweet birch are actually
mixtures of about 99 per cent, of the ester methyl salicylate vith
about 1 per cent, of other substances. Lavender, bergamot and
geranium oils are tjqDical oils wlficli owe their odour principally
to the presence of esters. In most cases where an essential oil
contains esters, one particular ester predominates, but small

204

PERFUMERl

quantities of subsidiary esters are usually associated with it.
Actually it is impossible to determine the amount of each ester
separatel3’', so that it is the conventional practice to retirni the
esters in an analysis calculated from the saponification value (see
belov,’) in terms of the predominatmg ester. For example, the
expression that lavender oil contains 40 per cent, of esters means,
in fact, that if all the esters were truly iinalyl acetate, the amount
would be 40 per cent., whereas, in fact, there may be 38 per cent,
of true Iinalyl acetate and 2 per cent, (more or less) of other esters.
The fact that the determination of esters is a comparatively easy
one^ to make has caused an exaggerated value to be placed upon
the esters in certain essential oils. Tliis is a tendency amongst
analysts wliich is difficult to combat. Where a given constituent
can be accurately determined in a natm-al substance, the deter-
mination maj’- be of the highest importance in assisting iii deciding
whether the substance is pure or adulterated, but it does not, of
course, follow that the value of the substance is in direct pro-
portion to the easily determined constituent. It is the failure to
sufficiently distinguish these proportions that has led to an over-
statement of the value of esters by those who maintain what is
commonly called the “ ester theory.”

It is customary — and rightly so — to assess the value of certain
essential oils solely on the percentage of esters they contain. For
example, bergamot oil so nearly completely owes its odour value
to the linaljd acetate it contains that the oil is properly valued
on the basis of its ester content. But this is far from true in the
case of lavender oil, although the extreme advocates of the “ ester
theory ” insist that this is the proper basis of valuation. But
lavender oil owes its odour value to various bodies, and not to
its Hnalyl acetate alone ; so that it is quite unsafe to value the
oil only on this criterion. To illustrate this, it is only necessary
to draw attention to the fact that English lavender oils never
contain more than about 8 to 10 per cent, of esters, wliilst French
oils contain up to 40 per cent, and over ; and there are extremely
fine oils produced on the' Italian frontier containing only from
25 to 30 per cent, of esters, which are of finer odom’ value than
some French oils containing 40 to 42 per cent, of esters. Many
factors must be taken into account in valuing such oils. The
altitude at which lavender grows has considerable influence on
the amount of spike lavender found in proximity to the true
lavender and the consequent hybridisation takmg place ; and as
spike lavender oil is practically free from esters, it is probably

205

PEBFU MFjBY

true that the ester determination affords a fairly accurate basis
for valuing oils distilled from plants grown in the same neighbour-
hood.

The esters in an essential oil are determined in the following
manner. Trom 2 to 5 grams of the oO, according to the amount
of esters expected to be present, are weighed into a small flask
of about 250 c.c. capacity, and 10 c.c. of alcohol and a few drops
of phenolphthalein solution added. Semi-normal solution of
caustic potash in alcohol (of approximately this strength) is added
drop by di-op until the free acids present in the oil are neutralised.
Twent 3 ’--five cubic centimetres of the alkaline solution are then
added and the liquid boiled under a reflux eondenser for one
hour’. A “ blank ” test, that is, 25 c.c. of the alli:aline solution
without the oil, is carried out at the same time. The contents of
the flasks are then diluted with 100 c.c. of w^ater and titrated
with semi-normal hj’-drochloric or sulphuric acid. The difference
between the two titrations gives the amount of alkali that has
been used for decomposing the ester present in the oil. Not more
than about half the alkali used should have taken part in the
reaction. If substantiaUj’^ more than this has been used up, the
determination should be repeated, using either less of the sample
or more of the allcaline solution. The number of milligrams of
KOH used to saponif}^ 1 gram of the oil is termed the ester number.
From this value the pereentage of esters, expressed in terms of

M X A

any given ester, can be calculated from the formula — =

560

percentage of ester, w^here M is the molecular w^eight of the ester
and A is the ester number.

In order to save tedious ealculations, a table has been prepared
by Messrs. Scliimmel ch Co. whieh gives the amount of esters for
every value usually obtained, m terms of the usually occurring
esters, such as linalyl acetate, citroneltyi acetate, sesquiterpene
alcohol esters, and geranyl tiglate. (These tables are reproduced,
by permission, in “ The Chemistrj’- of Essential Oils ” (E. J. Parry),
vol. ii., 4th ed., pp. 323-333, q.v.) The detection of artifleial
esters is the subject of a separate monograph {q.v.). ■ Although
most of the following artificially prepared esters and their corre-
sponding alcohols are described separate^ elsewfliere, the follow'-
ing summary of their odour characters by Prins and Sclnvarz
(P. cfc E. 0. R., 1916, 335) may be usefully given here : —

Benzjd alcohol : Odour not very strong, slightty bitter ;
reminds of benzaldehyde.

20Q

PEBFU MERY

Beuz3'l formate : Odour very strong, svect, pungent ; reminds
of cinnamic alde]i3’dc.

Bcnzji acetate : Odour strong, fruity jasmin odour ; rather
pungent.

Benz \-1 propionate : Flover odour vith a fruitj* freshness ; ver3'’
useful for liner soaps.

Bcnz3'l but3’rnto : Sweet fruity odour (ajiricot).

Benz3d valerianate : Flower odour ; reminds of the esters of
phcjnd-etln-l alcohol.

Phen3*I-cth3’l alcohol : lias the well-known sweet rose odour ;
reminds of hcnz3*l alcohol.

I?hen3’l-eth3'l formate : Has the sweet pungent odour of the
chr3’santhemum type.

Phen3'l-eth3d acetate : Bose odour of the red rose type ; very
much in use.

PEeiyd-etlyd propionate : A fine rose odour of the fruity
ty-pe.

Phen3d-eth3d but3Tate : A fine distinctive rose odour with a
tinge of a leaf-lilce odour.

Phen3d-eth3d valerianate : Has a distinctive rose leaf odour.

Phen3d-i)roi)3d alcohol : As 3’^et rather unknown! and high in
price ; the odour combines the rose type of phen3*l-eth3d alcohol
with the heavier h3-acinth t3T)e of einnam3d alcohol.

Phen3d-prop3d formate ; Has a characteristic formate odour of
the heav3’', sweet honc3’’ and cinnamon t3^e.

Phen3d-prop3d acetate : Kemmds of geran3d acetate, but has
a characteristic flower odour. The cmnamon odour is not present.

Phen3d-prop3d propionate : Has a heav3'' and sweet fruity odour.

Phen5d-prop3d but3T:ate : Reminds of benz3d but3Tate, but the
odour is not so pungent, though ver3’ characteristic.

Phen3d-prop3d valerianate : Hcav3'’ odour, not ver3>- strong.

Cinnamyl alcohol : Has the well-knowm slight h3'acinth
odoiu- ; reminds slightly of cinnamon.

Cinnam3d formate : Has a very sweet characteristic formate
odour.

Cinnam3d acetate : Plo!ver odour, sweet and without cinnamon
odour.

Cinnam3d propionate : Odour of the fruity order,

Cinnam5i butyrate : Odour reminds of phen3d-eth3i but3uate,
but heavier.

Cinnamyl valerianate : Very characteristic rose odour, of the
tea rose t3^e.

207

PERFUMERY

Geraniol : The well-known rose-geranium-like odour, not very
sweet.

Geranyl formate : Eose leaf odour, as yet not extensively used,

Geranyl acetate : Flower odour of the rose with a leaf
odoim, not characteristic ; it is the geraniol ester chiefly in use.

Geranyl propionate : Highly characteristic rose odour, fresh
flower odour.

Geranyl but 3 a’ate : Sweet odour of the fruity type, reminds
strongly of fresh apples [reinettes cVor).

Geranyl valerianate : Odoim fruity, reminds of the acetate, not
characteristic.

Citronellol : Has a distinct, sweet characteristic rose odom-, much
more pronounced than the odom* of geraniol.

Citronellyl formate : A characteristic formate odour, sweet and
more rose-lilce than geranyl formate.

Citronellyl acetate ; Eeminds very much of phen 3 d-eth 3 d
acetate, flne rose odour.

Citronell 3 d propionate ; Exceedhigly sweet and lastmg rose
odour of the heav 3 '- and Oriental kmd.

Citroneltyl but 3 T:ate : Sweet rose odour, more flower-lilce and
less fruit 3 ^ than geranyl but 3 a’ate,

Citronellyl valerianate : Eose-like odour, but not strong.

See also “ Artiflcial Esters.”

ESTRAGOL. — Estragol, or meth 3 d chavicol, CioHjoO, is the
principal constituent of estragon or tarragon oil, and is also found
in anise bark, bay and femiel oils. It is a highly odorous oil of
specifle gravity 0-972 ; refractive index, 1-5220 ; and boiling
point, 21 G°. This body is responsible for the flavour of tarragon
vinegar, in which the herb is used, as it is in wines of the Vermouth
type. It is not used to an 3 ’^ extent in perfumeiy jDroper.

ESTRAGON OIL. — Estragon or tarragon oil is an essential
oil employed m the manufacture of wines, and in aromatic
vmegars. It is distilled from the flowering herb Artemisia Dra-
cuncuhis, the 3 deld being from 0-25 to 0-8 per cent, on the dried
plant. It is a colourless or pale yellovdsh-green oil, with an odour
recalling that of aniseed, and having the following characters :
specifle gravity, 0-900 to 0-945 ; optical rotation, -f 2° to fl- 9° ;
refractive index, 1-5020 to 1-5140 ; acid value, 0 to 1 ; ester-
value, 1 to 9 ; and ester value after acetylation, about 15. Roure-
Berhxnul Fils, however, have found a sample, distilled by them-
selves, with the abnormal specific gravity 0-981. The oil contains
much mcth 3 i-chavicol (estragol).

208

PERFUMERT

ETHYX< ACETATE. [Magnolia oil contains a very small
quantity of ethyl acetate CII3.COO.C2H5. It has a very fruity
odour, but is^ very soluble and very volatile, so that it does not
play^ a very important part in perfumery. It boils at 76°. Its
specific gravity is 0’906 to 0’907, and refractive index 1-373.

ETHYL-AMYL-GARBINOL. — ^This body is one of the
isomeric octyl alcohols, of the formula CH3(CH2)4.CH(0H)(C2H5).
It occims naturally in oil of Japanese peppermint, and has been
prepared artificially by Pickard and Kenyon {Jour. Cham. Soc.,
1913, 103, 1923) by passing the vapour of a mixture of 145 grams
of normal caproic acid and 180 grams of propionic acid through a
tube charged with thorium oxide at 400°. The ethyl-ainyl-
ketone so obtained is reduced to the alcohol by moist ether and
sodium.

The alcohol has also been synthesised by Schimmel c& Co.
{Report, Aprfi, 1912, 102 ; April, 1913, 82).

The following are the characters assigned to it by the chemists
quoted : —

Pickard and
Kenyon.

Schimmel & Co.

Boilmg point

168°-172°

178-5°-179°

Specific gravity

90°

0-8247 at ~

0-8276 at 15°

Optical rotation

Refractive index

Melting point of acid phthalate.
Melting point of semicarbazone .

4- 6-79°
1-4252
66°-68°

112°

-}- 6-43°
1-4275
65-5°-66°
117°

ETHYL-AMYL KETONE.— This body, C2H5(CO)(CH2)4CH3,
occims naturally in Erench lavender oil. It is an aromatic oil,
having a specific gravity 0-825 ; boiling point, 170° ; and refrac-
tive index, 1-4154. On oxidation it yields normal caproic acid.
It forms a semi-carbazone melting at 117° to 118°.

ETHYL ANISATE. — ^This body is a crystalline body, of the
qrmula C6ll4(0CH3)(C02.C2H5).. It has a fine odour of chervil.

^THRANILATE.-This ester, C5H4.(im2)
(LUgOgHs) IS a very odorous liquid boiling at 260°. It occurs in a
few essential oils, and is of fine neroh odour. It closely resembles

*’• 209 14

PERFUMERY

methyl antliranilate {q.v), but is rather sweeter and softer in
perfume, and does not discolour so readily. It can be prepared
artificially by the action of hydrochloric acid on ethyl alcohol and
anthranil-carbonic acid (isatoic acid). It is useful in artificial
neroli and jasmin.

ETHYL BENZOATE.— This ester, C 6 H 5 .COO.C 2 H 5 , is not
a natural constituent of any essential oil, so far as at present
known. It is used in the preparation of artificial ylang-ylang and
similar flower oils, and is used generally for the same pimposes
as the corresponding methyl ester, which is known as niobe oil.
It is prepared artificially by the condensation of ethyl alcohol and
benzoic acid by means of hydrochloric acid. It is a sweet-smelling
oil, which has the following characters : specific gravity, 1-0502
to b0530 ; refractive index, 1-5050 to 1-5063 ; and boihng point,
212 °. It is soluble in 2 volumes of 70 per cent, alcohol and in
7-5 volumes of GO per cent, alcohol.

ETHYL BUTYRATE. — ^Pineaj)ple essences invariably con-
tain this most useful fruit ester, a liquid boiling at 121 °, of fine
fruity odour. It has the formula CH 3 (CH 2 ) 2 COO.C 2 H 5 . It is
useful in minute quantities for modif^^fing artificial rose and similar
odours. The commercial ai-ticle consists of a mixture of isomers,
with a boiling range from about 115° to 140°. It is never a very
pure article.

ETHYL CAPROATE. — ^This ester (ethyl hexoate) is occa-
sionalty used for its fruity odour. It has a specific gravity 0-877 ;
refractive index, 1-4075 ; and boils at 167°.

ETHYL ^ CAPRYLATE. — ^Ethjd caprylate (eth 3 d octoate)
CH 3 (CH 2 )cCOO.C 2 H 5 is an ester having an odour recalling that
of secondary products of vinous fermentation. It is probably a
constituent of oil of cognac, and is useful in modifying floral
bouquets. Its specific gravity is 0-873 ; refractive index, 1-4171 ;
and boiling point, 208°.

ETHYL CINNAMATE. — ^The cinnamic ester of ethyl

alcohol C 6 H 5 .CH : CH.COOC 2 H 5 is not often found naturally,
but is a constituent of the essential oils of Kaempf&ria galayiga and
Stoi ax. It is prepared artificially by passing a .current of dry "
hydrochloric acid gas thi'ou^ an alcoholic solution of cinnamic
acid. It is an odorous liquid, optically inactive, solidifying on
cooling, and melting at 12 °. It has a specific gravity 1-050 at 20 °

210

PERFUMER T

refractive index, 1-5590 ; and boiling point, 271°. It is useful in
sweet, heavy bouquets of the Oriental type, and also in eau de
Cologne where a heavy, persistent sweet tone is desired.

ETHYL CITRATE.— See » Esters, Artificial.”

ETHYL-DEGINE-GARBONATE.— This new synthetic is
analagous to the corresponding heptinc-carbonate. Its -formula
is CgHi^.C i C.COOCjIIg. It is an oil having a “ leafy ” perfume,
.recaUing that of mignonette, in which type of perfume it is of
considerable value .-

ETHYL DEGYLATE. — ^The ethyl ester of capric, or decylic,
acid, CH 3 (CHo) 8 C 02 C 2 H 5 is a synthetic perfume, prepared by the
esterification of capric acid, which is present in cocoa nut oil,
with ethji alcohol. It has a floral odour and is useful in artificial
rose perfumes.

ETHYL FORMATE. — ^This ester resembles ethyl acetate in
general characters, but has a rather sharper odour. It is a liquid
of specific gravity, 0-926 ; refractive index, 1-3600 ; and boiling
point, 55°.

ETHYL-HEPTINE-GARBONATE.— This expensive sub-
stance, CgHij.C ; C.COOCgHg, is one of the most recent sjmthetic
perflunes, having what is known as a “ green leaf ” effect, espe-
cially in the modification of the ipxixe flower effects in violet and rose
perfumes. {Vide Amyl-heptinc-carbonate.)

ETHYL HEPTOATE. — Oenanth 3 ^hc ether is the common
name for this ester. It has a fragrant odour recaUing that of the
secondary constituents of vinous fermentation. It is sold in a
nearly pure condition as artificial oU of cognac. It is an oil
boiling at 188°, and is used to a limited extent in the manufacture
of artificial flavouring essences, and in artificial flow^er extracts.
Its specific gravity is 0-871, and refractive index 1-4140.

ETHYLISOAMYL-OXY-BUTYRATE.—Thisester, recently

synthesised by Bogert and Slocum {American Perfumer, xviii.,
12, 621), possesses a fine fruity odour. The free acid wdien
distUled under reduced pressure gives isoamylbutyrolactone, an
oil boilhig at 131° to 134° at 12 mm., having a fine odoii of
peaches. '

ETHYL LAURINATE. — ^This ester is used in very small
quantities in the preparation of artificial flower perfumes, such as

211 14-2

PERFV M E R I

mignonette and tuberose. It is an oil of very sweet, fruity odour,
and of intense strength. It boils at 269 °, and has the formula
CH3(CH2)ioCOOCoH5.

ETHYL MALONATE. — ^Blalonic other, as the diethyl ester
of inalonic acid is usuall}^ termed, is of great value in general
S3nithetic chemistiy, but has also recently been recognised as a
useful artificial perfume. Its odour is fruity, recalling that of
apples, but much sweeter than that of the valerianic ester. It is
prepared bj’' treating either potassium cj^'anacetate or malonic acid
with ethjd alcohol and hydrochloric acid. It is an oil of specific
gravit}^ 1 - 070 , and boiling at 198 °. Its formula is CH2(C0002H5)2.

ETHYL MYRISTINATE. — This ester is a semi-solid body,
melting at 11° and boiling at 295 °. Its formula is CH3(CH2)i2
COOC2H5, and it is jnepared bj'- the esterification of m3n’istic acid
and eth3d alcohol b3>- means of h3’drochloric acid. It is of powerful
and persistent odour, and is useful both as a fixative and in
modif3mg floral odours, especial^ violet perfumes.

ETHYL-OCTINE-CARBONATE.— This is still an experi-
mental S3nithetic. It is analagous in all respects to the correspond-
ing heptine-carbonate. Its formula is CgHi3.C | C.COOC2H2.

ETHYL OLE ATE. — ^Ethyl oleate is an ester principal^ used
as an “ arificial ” ester for adulteration purposes. {Vide “ Esters,
Artificial.”) It has, however, a slight floral odour, and also fixative
properties. It is a liquid of the formula CjL7H33.COO.C2H5,
boiling at about 340 °.

ETHYL PELARGONATE. — ^This ester (eth3d nonylate),
of the formula CH3(CH2)7COOC2H5, is a very fragrant oil made b3''
melting undec3denic acid with caustic potash, and setting free
the resulting pelargonic acid b3’- dilute sulphuric acid. This acid
is then esterified with eth3d alcohol in the presence of sulphm-ic
acid, and purified b3’' fractional distillation. It boils at 100° to
110° at 10 mm. pressure, or at 228 ° at normal pressure. It has a
specific gravity 0 - 876 , and refractive index 1 - 4255 .

ETHYL -PHENYLAGETATE.— This ester is formed by the
condensation of eth3d alcohol and phen3d-acetio acid. It is a very
sweet smelling oil with an odour recalling honey and roses. It
is ver3'' useful in compounding artificial rose odours. Its formula
is C6H5.CH2.COOC2H5. It has a specific gravity about 1-0366 ;
refractive index, 1-4990 ; and boils at 227 °.

212

PERFU ME R1

ETHYL PHTHALATE. — As a perfume ethyl phthalate lias
no Talue. It is, however, of considerable ser\dce as a solvent for
artificial mnsk, and has also a fixative value. Its principal use,
however, is as an “ artificial ” ester for the purposes of adultera-
tion. It is a liquid of specific gravity, 1-124 ; refractive index,
1-5020 ; and bods at 293°. One per cent, indicates, in- the usual
method of anatysis, 1-77 per cent, of linahd acetate. Its formula is
CgH 4 (COOC 2 H 5 )o. It is prepared by the esterification of phthalic
acid ^vith eth}-! alcohol.

ETHYL SALICYLATE. — ^The usual artificial wintergreen oil
is methyl salic 5 date {q.v.). The eth}*! ester, CcHj.CHg.COOCoHs
is a liquid boiling at 234° ; of specific gravity, 1-1372 ; refractive
index, 1-5234 ; and optically inactive. It sohdifies at low tem-
peratimes, and melts at 1-3°. It is an oil having a very fine vdnter-
green odour, more dehcate than that of the methyl ester.

ETHYL SUCCINATE. — Succinic ether has no legitimate
use in perfumery, but is used as an “ artificial ” ester for adultera-
tion purposes. It is an oil boiling at 216°, and has a specific
gravity 1-044. One per cent, appears in tlie usual method of
analysis as 2-26 per cent, of linalyl acetate. It results from the
esterification of succinic acid and ethyl alcohol.

ETHYL VALERIANATE. — ^This ester, C 4 Hg.COOC 2 Hg is an
oil with a powerful fruity odour. It results from the esterification
of valerianic acid and ethyl alcohol. The commercial article is a
mixture of isomers, of specific gravity about 0-875 ; refractive
index, 1-3980 ; and boding point, 135°.

EUCALYPTOL. — ^This body, or cineol as it is more scien-
tificaUy tei’med, is the characteristic constituent of the majority
of the eucaljq)tus ods. There are, of course, a certain number of
the ods of this species which are free, or practicaUy free, from this
constituent. The eucatyptus oils which contain eucalyptol are
used to some extent in perfumery, but rather as antiseptics than
as pleasant odour bearers. Eucalyptol is an oxide, of the formula
CioHigO, having a specific gravity 0-930 ; refractive index,
1-4590 ; melting point, -f 1° ; and boiling point, 176° to 177°.
The usual process for the determination of eucal 3 rptol in eucalyptus
and other ods containing eucalyptol is that devised by Scammel.
This, as used to-day, is carried out as follows. To a known weight
(about 5 grams) of the od, from 1 to 1-5 times its weight of
phosphoric acid, of specific gravity 1-75, is slowly added, drop by

213

PERFUMER Y

drop, with continual stirring, the mixture being kept cold all the
time. The ciystalline magma Avhich results is strongly pressed
between filter paper after as much as possible of the terpenes
present has been drained ofi. The cr^^stalhne mass is, after
repeated pressing, decomposed by hot water in a flask with a
graduated neck, and the hberated eucalyptol measured off in the
neck. There are several other methods of determination of
eucalyptol, but the only one possessing any merits comparable
Avith those of the original phosphoric acid method is that devised ■
by Cocking (P. & E. 0. R., 1920, 281), and varied by Wallcer.
This method is a physical one, and depends on the determination
of the freezing point of a mixture of the oil eontaining eucalyptol
and or//m-cresol in proportions corresponding approximately with
the molecular weights of the two substances; A stout-walled
tube suspended by a AAire loop to the balance is used for the
determination. Into this is AA^eighed 3 grams of the oil and
2- 1 grams of melted or/^o-cresol. The tube is then removed from
the balance and inserted through a bored eork into a Avide-^
mouthed bottle containing water, which can be heated or cooled
as necessary. The mixture is agitated, and the sohdifying point
noted. It is then warmed until melted, and the solidifying
point again noted. This process is repeated until the sohdify-
ing point becomes constant. With a pm’e or^/m-cresol melting at
30° the folloAving results were obtained Arith mixtures of known

eucalyptol content : —

Per cent, of

Freezing points (varying accordinj

eucalyptol.

tlie nature of the admixtrrre).

100 .

. 65-2°

96 .

. 63-4°-53'6°

90 .

. 51-2°-51-7°

85 .

. 48-5°-49-7°

80 .

. 45-8°-47-7°

75 .

. 43-2°-45-7°

70 .

. 40-6°-43-8°

65 .

. 37-4°-41-2°

60 .

. 34-2°-37-4°

65 .

. 29° -33-6°

50 .

. 25-4°-29-8°

45 .

. 22-2°-26-2°

Walker {Jour. Soc. Ghem. Ind,, December, 1923) prefers the
use of a-naphthol to o-cresol in the freezing point determination,
on account of the non-hygroscopic nature of the compound. This
modification has been criticised by Cocking (P. Js E. 0. R., 1924,
10), who states that : —

214

PERFUMER Y

“ (1) In the crcsineol method the freezing point is the tempera-
ture at wiiich the solid cresineol separates from the mother liquor,
which latter consists of a saturated solution of cresineol in a
mixture of the non-cineol portion of the oil, and o-cresol in
vnvarying proj)orlwns.

“This mixhna is gjcrmaneiithj liquid at ihe icmqjeraiure of the
test.

“ (2) In Wallcer’s proposed modification the freezing point is
influenced by the crystallising out of the a-naphthol in addition
to the a-naphthol-cineol compound, and thus the mother liquor
will consist of the non-cincol portion of the oil saturated with
a-naphthol and •with the a-naphthol-cineol compound, the relative
proportions of -which v'ill vary with the temperature. It is thus
apparent that, while this modifled method may give fairly accurate
results on oils containing from 100 to 50 per cent, of cineol, it
cannot be relied upon, as the freezing points obtained vdth such
oils are also given by oils containing from 0 to 50 per cent, of
cineol.”

For other methods of determining cucal 3 q;)tol, see “ The
Chemistry of Essential Oils, etc.” (E. J. Parry), vol. ii., 4th ed.,
p. 270.

EUCALYPTUS CITRIODORA. — ^This tree is kno'UTi as
the citron-scented eucalyptus, and is found along the coast of
Queensland and as far south as Port Jackson. It has been stated
to be a variety of the New South Wales spotted gum. Eucalyptus
maculaia, but it is considered by Baker and Smith to be a separate
species. The essential oil is well known, having been on the
market for some years. As the tree is a tall one, the cost of collect-
ing the material for distillation is high, and as the yield is only
about 0-75 per cent., the cost of the oil is at present rather out of
proportion to its perfume value as compared with other oils of
-the same type of odour. It is so rich in citronellal that it is
undoubtedly the best source (apart from questions of price) of
that body, and citronellol produced therefrom is said to be superior
to that from any other source except LepiospermuTn ciiratuin.
And since it is possible, bj’' fractional distillation only, to raise
the aldeh 3 '^des to 98 per cent., thej>' can be reduced directly,
without the expense of previous separation by means of their
bisulphite compounds. The tree has been extensively cultivated
in private gardens in and around Sydney for ornamental pur-
poses. In its native state it has never been found further
south than Bundaberg, in Queensland. The oils from the wild

216

PE RFU MEET

and the cnltivated trees hare given the following results on
distillation : —

Wild.

Cultivated.

Specific gravity

0-S64r-0-905

0-861-0-8C6

Optical rotation •

— 1° to -f 2°

0°to - 1-15°

Refractive index

1-4540-1-4678

1'4498-1-4515

Citronellal

Up to 95 per cent.

95-98 per cent.

It also contains traces of geraniol and puiene. It is far more
dehcate in odour than any type of citronella oil. The tree much
improves hy cutting, and if cultivated as a small tree the leaves
can be collected at a cheap rate. Many cultivated trees have
been found to jield well over 1 per cent., even up to 1-5 per cent.,
of oil, which is a great increase over that obtained from the wild
trees. The small trees can be cut when they are from three to
five years old. The cultivation of this tree on a commercial scale
would probabl}' be exceedingly remunerative, and allow the oil
to compete successfully with Java and Bm’mese citronella ojls.
[Vide Bulletin No. 5, Technological Museum, Sydney, N.S.W.,
1923.)

EUCALYPTUS MACARTHURI, OIL OF.— Amongst the
perfume-bearing oils recentl}’’ examined, and which are derived
from raw material grovm in the British Empire, that of Eucalyptus
Macarthuri is one of the most remarkable, and is worthy of
very considerable attention. The oil is at present almost entirely
consumed locally in Australia as a denaturant of alcohol for
perfumery pm’poses. It is an oil which is extraordinarily rich
in geranjd acetate, so much so that, by skiKul manipulation,
gerany] acetate of 80 to So jDer cent, strength, the balance being
principall 3 ’ free geraniol, can be jDroduced from it without acetyla-
tion. As the species is somewhat sparsely distributed, attempts
have been made to cultivate it in Australia, and, being one of
the apparently stable species, the oil seems to remain constant in
composition. There is a plantation at Emerald, in Victoria,
started in 1911, which has given good results. A sample of the
oil distilled by Penfold (Bulletin No. 5, Technological Museum,
Sydney, N.S.W., 1923) from leaves of plants gro%TO at CrojMon,
near Sj'dney, from seeds collected by Dr. Guthrie, gave the
following results on analysis : jfield of oil, 0-26 per cent. ; specific

216

PERFUMERY

gravity at 15°, 0-9274; optical rotation, +3-1°; refractive
index, 1-4744 ; and geranjd acetate, 67 per cent. Trees grovTi at
Longueville and Aslifield from seedlings taken from Croydon gave
essential oils wliick 3 delded the following results on anatysis : —

Yield of oil per cent.
Specific gravity .
Optical rotation .
B.efractive index .
Esters as geranyl acetate
Free geraniol
Eudesmol

Longueville.

0-2

0- 9255
+ 3-2°

1- 4692

74-8 per cent,

Ashfield.

0-74

0- 9257
+ 3-5°

1- 4696

70-2 per cent.

The trees can be cut for distfilation every year and yet produce
their full quantity of leaf for next year’s cutting. By keeping
them as small trees they 3 deld more fohage, and the cost of
collection is less. Moisture is essential, but the tree vdll grow in
poor soil, although a good soil will cause an increased yield of oil.
The oil has been recommended as a source of geraniol, though, as
this requires a preliminary saponification, it is probable that the
cost would be prohibitive ; but as a source of geranyl acetate the
tree would probably amply repay careful cultivation.

EUCALYPTUS PIPERITA. — This species of eucalyptus
may be of considerable commercial importance as a source of
supply for piperitone, if this substance should, as hoped, prove
a suitable raw material for the manufacture of thymol or menthol.

It is (“ A Research on the Eucalyptus,” Baker and Smith, 2nd
ed., 274) a tail tree with a fibrous bark, found round Sydney and
in Victoria and Queensland. The account of the yield and
characters of the essential oil distilled from the leaves and terminal
branchlets in 1897 given by Baker and Smith {loc. cit.) has quite
recently been supplemented by Penfold and Morrison [Jour, and
Proc. Roy. Soc. N.S.W., Iviii., 1924, 124).

It is pointed out that Baker and Smith gave the yield of oil as
0-8 per cent., the oil, on distillation, yielding 85 to 86 per cent,
distilling below 200°. Although there is no record of the quantity
of piperitone present in this species, it could not have been more
than 5 to 10 per cent., and this has usually been assumed to be
the case. Many inquhies have been made by persons clearing
their property of this species for information regarding the oil,
and they were advised according to the foregoing results. Field
observations made by Penfold and Morrison during the past
few years, however, led them to suspect that the trees of this

217

PERF U MER Y

species growing around Port Jackson contained much more than
the published yield of oil (0-8 per cent.), and, from the odour of
the crushed leaves, that piperitone was present in considerable
quantitj". Consequently, they decided to reinvestigate the matter,
and material was collected from such places as Longueville,
K^higai, Como, etc., with the result that field observations were
confirmed. The leaves and terminal branchlets, cut as for com-
mercial distillation, collected about the same period of the year,
March-April, and weighed when fresh, yielded from 2 to 2-5 per
cent, of oil, containing 40 to 60 per cent, of piperitone. The oils
thus obtahied closely resembled those from E. dives, so much so
that it is doubtful if an unlabelled specimen of each could be
difierentiated. These results are especially interesting, as they
confirm in a very striking manner the observation of Surgeon-
General White made in the '' Journal of a Voyage to New South
Wales,” pubhshed in London in 1790, that the name of “ Pepper-
mint Tree ” had been given to tliis plant on account of the very
great resemblance between its essential oil and that of the Enghsh
peppermint, Manilla ‘pi-parita. Such a description would appear
most unlikely if the oil had resembled that described by Messrs.
Baker and Smith, where the piperitone content did not exceed
10 per cent. These authors state, in the work mentioned, page 274,
under Pemarks : “ In this research particular interest pertains
to tliis species, as it was from trees of the’ ‘ Sydney Peppermint,’
growing where Sydney now stands, that the first eucalyptus oil
was obtained. It was distilled by Dr. White, Surgeon to the
First Fleet, in 1788, and it seems remarkable that they did not,
at the time of their investigation, examine the oils from trees
grovdng in or around Sydney as well as those from fifty to 100
^ miles away. It is probable that the 'composition of the oil,
described below, closely resembles that first distilled in 1788.”

In view of the disparity between Baker and Smith’s results
and those now recorded, Penfold and Morrison have carried out
a considerable number of observations and experiments on oils
obtained from this species growing in various locahties and
altitudes, and have come to the conclusion that, apart from slight
variations likely to be due to the influence of ecological conditions,
there are two very distinct forms of this tree, one growing
close around Sydney — ^say, the Port Jackson district — ^ 3 delding
2 to 2|- per cent, of oil containing 40 to 60 per cent; of piperitone,
and the other ^fielding only 0-6 to 0-8 per cent, of oil low in
piperitone, but high m phellandrene and eudesmol, and containing

218

PERFUMER T

up to 20 per cent, of cineol, found principally in the more moun-
tainous districts. This latter is tentatively termed the mountain
form, or variety “ A,” to distinguish it from the typical form.

The type E. piperita and its varied forms are being carefully
studied, and the final result of their observations will be dealt
with in a later publication. Meanwhile, they prefer merely to
direct attention to the strildng difference in the composition of
the oils of two very distinct forms, and to the interesting nature
of that obtained from trees grovdng at Port Jackson, the chemical
and physical constants of which are totally different to anj-thing
that has previously been published concerning the oil of this
species.

In the table particulars are given only of the oils from the Port
Jackson trees, those from other localities being left for a later
communication.

The oils distilled by Penfold and Morrison had the following
characters : —

18/3/1924

29/3/1924

8/4/1924

Locality,

LongueviUe
Kuringai
Como. .

Lbs.

Specific

Gravity

0-8924

0-9016

0-8977

Optical notation. Refractive Index, ®°™A/cohoV“ Kperitone Content,

Per cent.

— 64-60

— 52-00

— 62-75

1 in 9
1 in 5-6
1 in 5-3

These oils on distillation yielded, on an average, 40 per cent,
distilling at 60° to 75° at 10 mm., 18 per cent, at 75° to 100°, and
42 per cent, at 100° to 110°.

Separation of Phellandrene and Piperitone. — The portion distil-
ling at 60° to 75° at 10 mm., on fractionation, readily yielded
pheUandrene of boiling point 59° to 61° at 10 mm., having a
specific gravity at 15°/15° of 0-8467 ; optical rotation, — 93° ;
and refractive index, 20°, 1-4729. The last fraction (boiling
point, 100° to 110° at 10 mm.) was found to consist principally
of laevorotatory piperitone having an optical rotation of — 57°.
On purification through the bisulploite compound, it possessed
the following characters : boiling point at 10 mm., 107° to 108° ;
specific gravity, 15°/15°, 0-9386 ; optical rotation, — 10° ; and

219

PBnFU MEBY

rofrnctive index, 20°, 1*4830. Cincol was not detected in tlie
terpene fraction.

The oil described bj!- Baker and Smith had the following
characters : —

Specific gravity ....

Optical rotation . . • ■ — - 2*7^

Refractive index .... 1*4781

Saponification value . . .11

EUCALYPTUS STAIGERIANA.— This tree is knowji
as the lemon-scented ironbark of Queensland. It is a medium-
sized tree, and so far has only been found in the Palmer River
district of north Queensland.

The oil was referred to by Schimmel ct* Co. as far back as 1888
{Semi-Annual Report). According to Baker and Smith, the
dried material j'ieldcd from 2*5 to 3 per cent, of oil having a specific
gravity 0*8715 ; optical rotation, — 38° ; refractive index, 1*4814 ;
and containing GO per cent, of ?cei‘o-limonene, 16 per cent, of
citral, the remainder being gcraniol, geranyl acetate, and a
.sesquiterpene. Two samples I’cccntly examined by Penfold
{Bulletin No. 5, Technological Mnscum, Sydney, N.S.W., 1923)
gave the following results : — ^ ^

Percentage yield
Specific gra%nt5'-
Optical rotation
Refractive mdex
Citral .

2*59 per cent. —

0*8777 . . 0*8822

— 34*G° . . — 26*4°

1*4793 . . 1*4797

28 per cent. 38 per cent.

This oil has been said by experts to be suitable for flavouring
confectionery in the place of lemon oil, and also to be suitable for
denatui*ing alcohol to be used for the manufacture of ean de
Cologne.

EUCALYPTUS STUARTIANA. — ^The eucalyptus oil from
this tree has an odour recalling that of apples. It contains
eucalyptol, pinene, and esters which have not been fully investi-
gated. It has a specific gravity 0*916 ; optical rotation, 4*7°‘;
and refractive index, 1*4780.

EUDESMOL.— This compound is a crystalline body, melting
at 80°, of the formula CisHacO, which is a sesquiterpene alcohol.
It was first isolated from the oil of EucalyiAus pigicrita by H". G.
Smith {Jour. Proc, Roy. Soc. N.S.W., 1899, 33, 86), and later
examined by Semmler and Mayer {BericJite, 1912, 45, 1390), and
Semmler and Tobias {BericMe, 1913, 46, 2026). It is a crystalline

220

PERFUMER r

bod.y melting at 78°, boiling at 156° at 10 mm., of specific gravity
0-9S84 at 20°, and refractive index 1-5160.

EUGENIA APICULATA, OIL OF.— The Cliilian plant
Eugenia ajnculala possesses leaves wlucli are used to a consider-
able extent as a drug. According to ScJn7mncI tfc Co. {Rejjorl,
October, 1910, 145), it yields 1-27 j:)cr cent, of essential oil having
an odour recalling that of myrtle. Its characters are as follows : —

Specific gi’avitj’ .... 0-892

Optical rotation . . . . -{- 12° 40'

Refractive index . . . 1-4782

Acid value .... 5-5

Ester value . . . .25-8

Ester value after acetylation . 65-3

EUGENIA GHEKEN, OIL OF— The leaves of Evgenia
c/fcA'c;?, aplant belonging to the natural order Myrlaccce, indigenous
to Chili, yield about 1 per cent, of an essential oil having a pleasant
odour recalling those of sage and eucal 3 rptus. It is of a yellowish-
green colour, and has the following characters : —

Specific gravity .... 0-8795

Optical rotation . . . . -{- 23-5°

The only constituents so far identified are pinene and cineol.

EUGENIA JAMBOLANA.— The seeds of this plant, a
member of the natural order Myriacecc and a native of the West
Indies, are knovTi as jambul seeds. Power and Callan {Pharm.
Jo7ir., 1912, 88, 414) have distilled the essential oil, which is
pale 3 'ellow in colour and ver}' aromatic. It has a specific gravity
20°

0-9258 at — -, and an optical rotation — 5° 42'.

20° ^

EUGENIA OCCLUSA, OIL OF.— Schimmd cG Co. [Report,
April, 1911, 123) have reported on an oil knovni in Java as “ salani
oil.” It is distilled from the leaves of Eugenia occhtsa, the yield
being about 0-05 per cent. Its properties are as follows : —

Specific gra^^ty .... 0-9567

Optical rotation . . . . — 1° 40'

Refractive index .... 1-4681

It contains citral and other aldehydes not yet identified.

EUGENIA UNIFLORA, OIL OF.— According to Peckolt
[Bericlite d. DeutscJi. Pliarjn. Ges., 1903, 13, 130), the seeds of
Evgenia uniflora yield about 0-043 per cent, of a yellowish essential
oil having an aromatic pepper-like odour. The leaves yield about
0-14 per cent, of a similar oil, of specific gra'sdty 0-963.

221

PERFUMERY

EUGENOL. — ^Eugenol, C 10 H 12 O 2 , is a phenol occurring in
oils of clove, cinnamon leaf, bay, pimento, and others. It is the
characteristic odour bearer of clove oil, in which it occm’s to the
extent of from SO to 95 per cent. It is used to a very considerable
extent as the rav'^ material for the manufacture of vanillin, and to
a small extent for the manufacture of isoeugenol. Both eugenol
and isoeugenol are necessary constituents of all carnation per-
fumes {ci.v.).

Eugenol is a pale yellowish oil of intense clove odour, having a
specific gravity 1‘070 ; refractive index, 1*5439 ; and boiling
point, 252° to 254°. It forms a characteristic benzoyl derivative
melting at 69° to 70°, and a dii5hen3durethane molting at 107°
to 108°.

Eugenol in essential oils is almost invariably determined by
absorption bj^ means of a solution of caustic soda {vide “ Phenols,
Determination of ”). A more elaborate method, which possibl}'’
gives more accurate results, is that devised bj’’ Thoms, wliich is as
follows. About 5 grams of the oil are weighed into a small beaker
and 20 gi'ams of a 15 per cent, solution of caustic soda added, and
then 6 grams of benzojd chloride. The mixture is well stirred,
and the whole eventually'’ sets to a solid mass, much heat bemg
evolved. To this mass 50 c.c. of water are added and the mixture
warmed on a water bath until the compound is completely melted,
the mixture well stiiTcd, and allowed to cool again. The clear
supernatant aqueous liquid is filtered off and the cry'^stalline mass
t-wice remelted and washed with 50 c.c. of water. The crude
benzoyl-eugcnol is then recrystallised from 25 c.c. of hot alcohol,
which is first passed through the filter in order to dissolve any
benzoyd-eugenol thereon. The liquid is cooled to 17° and the
ciystalline precipitate collected on a small weighed filter paper,
filtered, and washed with 90 per cent, alcohol, until the filtrate
measures exactly 25 c.c. The filter paper and ciystals are weighed
after being dried to constant weight at 100° G. To the weight so
ob tamed 0*55 gram is added to allow for the solubihty of the
benzoyl-eugenol in the 25 c.c. of 90 per cent, alcohol. From this
the weight of eugenol is calculated, the molecular weight of
eugenol being 164, and that of benzoyd-eugenol 268. This method
is not used, however, for commercial analysis.

EUPATORIUM, OILS OF . — Eupatorium foaniculaceum
is a herb knovm as dog fennel, and is distributed through the
northern parts of America. It ynelds on distillation an essential
oil of a golden j'-ellow colour and a pepper-like odour. Miller

222

PEItFU MERY

{Bull. Univ. of Wisconsin, 1914, 693, 7) lias examined a number
of samples distilled in Alabama, the jdeld of oil _being about
1 per cent. The principal constituent of the oil is the dimethyl
ether of th3nnohydroquinone. Born3d acetate, borneol, linalol,
phellandrene, and probabl3" sabinene, are present in the oil. It
has a specific gravity 0-919 to 0-9G0 ; refractive index, 1-497 to
1-507 ; optical rotation, — lG-7° to -}- 14-3° ; and contains from
4G to GG per cent, of th3-moh3-droquinone dimeth3’l ether. The
oil distilled from Enpaiorhmi triplinervc, a plant indigenous to
tropical America and found vild in other tropical countries, is
of similar compo.sition.

EURYANGIUIM SUMBUL. — This plant, also known as
Ferula Sv.vihul, possesses a highly odorous root, known as sumbul
root. On distillation it yields 0-2 to 1-7 per cent, of a viscid dark-
coloured oil having a musk-like odour. Its specific gravity is
0-941 to 0-9G4 ; optical rotation about — G° ; acid value, 7 ;
and ester value, 17 to S5. Its constituents have not 3^et been
investigated.

EURYBIA AROPHYLLA. — ^This tree is one of the natural
order Gomposiloi, and is confined to Australia, Tasmania, and
New Zealand. Its leaves have a very pronounced odour of musk ;
hence its popular name the “ silver-leaved musk tree.”

EVERNIA PERFUMES. — ^The extracts of mousse de chene
of commerce {q.v.) are obtained inier alia from Evernia furfuracea
and Evernia priinastri, lichens flourishing on oak and other trees.

EVODIA oils. ^The evodia trees belong to a genus of .small
rutaceous trees or sluaibs, mostly natives of tropical New Holland
and the Indian archipelago. Most of the species are veiy sweet-
scented plants. The best known are Evodia Uorlensis, a native
of the Friendly Islands and the New Hebrides, a plant whose
leaves are used by the natives to perfume coconut oil ; Evodia
simplex, and Evodia Ruiaecarpa, The oil distilled from Evodia
simplex in Reunion was found by ScMmmel <b Co. {Berichi.
October, 1906, 83) to have the following characters ;

Specific gravity at 15“ . . 0-8737

Optical rotation . . . . 13° 4'

Acid value . . . . . 2-1

Ester value . . . - . . IQ.4

Ester value after acetylation . . 63-3

The oil contains methyl-eugenol and a crystalline ly^drocarbon
melting at 81°. , -

223

PERFUMER Y

The essential oil distilled from the fruit of Evoclia Rufaecaiya
has been examined hy Asahina and Kashiwald {J our. Pharm. Soc.
Japan, November, 1915). These chemists isolated from it a
terpene wliich they termed evodene, which is allied to the olefinic
terpenes of which myrcene is a t3^pe.

EXCQECARIA AGALLOGHA.— This plant, which belongs
to the natmal order Eupthorhiaceoo is a higlily odorous tree, the
wood being used in Dutch East Indies as a fumigant under the
name Menengen. The heart-wood of young trees is the most
odorous, the wood of old trees becoming almost odourless as
resinification takes place. The constituents have not been fully
investigated, but an alcohol melting at 85° is present in the form
of an ester.

EXOTHEA GOPALILLO.— An oil distiUed in Mexico from
this tree known as copalillo oil has been examined by Roure-
Eertrand Fils {Bulletin, 1914-1919, 138). It is a dark yeUow oil
with an odour recalling that of linaloe oil. It had the foUovdng
characters : —

Specific gravitj’’ .... 0-8504

Optical rotation . . . . + 0° 50'

Acid value . . . .10-2

Ester value . . . . .13*1

EXTRACTION OF PERFUMES FROM PLANTS.—
The methods used for the extraction of the perfume material
from the plant are extremely variable. The methods themselves
are, in general, old-established in principle, but during the last
few decades scientific investigation has been brought to bear
upon the questions involved, and there has been a vast improve-
ment in the methods in which these processes have been applied.
Fifty j’-ears ago, distOlation, for example, was just distiQation,
and that was all. The effects of time, pressure, and temperature
were practically neglected ; esters were hardly known, and if
they were decomposed dming the process of distillation, so much
the worse for the resulting oil. To-day, knowledge of the characters
of the constituents of essential oils, and of the conditions under
which they are extracted in the most perfect condition, has
advanced to such an extent that many raw materials for per-
fumeiy are undoubtedly prepared in an ideal manner. At the
same time, one has to remember that many of the plants used
for the extraction of perfumes- grow wild, or are cultivated in
spots far distant from large towns and under such conditions that

224

PEEFUMER Y

the time occupied in transporting the raw material to an up-to-
date factory in a largo town would, if such transport were pos-
sible, cause the material to deteriorate to such an extent that the
resulting perfume would be largely spoiled. The most scientific
factories and apparatus can onl}- exist economieallj’ where there
is within reasonable distance a i^lentiful suppl^y of the raw material
to be treated. The majority of the natural perfumeiy materials
which arc employed to-daj^ are the result of distillation processes.
This method of production is dealt with under “ Distillation ”
(q.v,).

For the preparation of a certain number of essential oils, how-
ever, distillation is not a suitable process, the oil being sufficiently
altered by the exposure to heat and moisture to become of quite
inferior quality. These oils arc prepared bj’- a cold process of
expression. Still, other essential oils arc of such a delicate
character, and are present in such minute amounts, that no process
of distillation or expression is practicable. For this type of oil,
ho separation is, in cfTcct, possible on a commercial scale. The
perfume is extracted bj’- means of a solvent and marketed in
admixture with other substances extracted at the same time, as,
for example, in the form of absolutes, concretes, or pomades.
For practical purposes, then, the methods of separation of the
perfume materials from the plant may, apart from the collection
of exudations, such as in the case of oleoresins, etc., be grouped
in the above manner, namely, by (1) distillation, (2) expression,
(3) extraction by solvents. Of these, as mentioned above, distilla-
tion is treated under its own heading.

The typical expressed oils of interest to the perfumer are those
of lemon, bergamot, orange, and lime.

■The bulk of the lemon oil of commerce is produced in Sicily,
where it is prepared, practically entirely, b}’- either the Scorzeiia
or the Epxigna methods. Almost every other process which has
from time to time been introduced has been discarded, and the
older processes have not been improved upon. In the Scorzetta
process, the fruits (lemons and oranges) are cut into halves by a
sharp knife, either longitudinally or across. If the peel after
the expression of the oil is destined for candied peel, it is usual
to cut the fruits longitudinally. The pulp and juice are removed
as completely as possible. The peel is soaked in water for several
hours, which causes the cell walls to become stiller and enables
them to be more completely ruptured than would otherwise be
the case, so that the oil globules are more completely discharged.

P- ' 225 15

PERFUMER Y

The men who actually express the oil sit m front of an earthenware
jar, across which rests a bamboo stick, which supports several
sponges, one of which is cup-shaped. The operator presses the
peel into the sponge vdth one hand, the other hand pressing the
sponge. This is done several times, the peel being turned round,
so that as much as possible of the oil exuding from the burst oil
cells is absorbed b}'’ the sponge. Where the peel has been cut
longitudinally, round sponges are used in place of cup-shaped'
ones. The oil gradually collects in the jar, mixed with water,
pulp, etc. The water is allowed to separate, and the oil is stored
in a cold cellar, filtered, and stored- in coppers or tins. The.
so-called Spugna method diflfcrs only from the above described in
details. The peel is removed by three longitudinal incisions, the
inside of the fruit remaining intact for after-Jreatment for the
lemon juice. It is quite obvious that an essential oil prepared
in tliis, or in similar manner, is not quite accurately described as
an essential oil. It is really an essential oil holduig in solution
such dissolved substances as are present m the peel, and which
have become dissolved in the oil. Hence, all such oils contain a
fixed non-volatile residue when evaporated on the water bath,
consisting of such solid or semi-solid dissolved substances.

The so-caUed Ecudle method was formerly used in Nice and
the neighbourhood, but is hardty ever employed to-day, except in
the West Indies for the production of hand-pressed oil of limes.
The process consists in causing the fruits to be roUed about m
cup-shaped vessels the bottom and sides of which are covered
with metal (brass, as a rule) needles. The oil cells are punctured,
and the oil, with some watery liquid, graduallj'^ collects in a
tubular extension of the vessel, and is collected and filtered
as usual. The “ Machine ” process is practically confined to the
expression of the oil from bergamot fruits. The most general
mechanical appliance used is a primitive hand-worked macliine,
in which the round fruits are rotated between discs provided
with either needle points or knives, suitable arrangements
being made for the collection of the oil which exudes from
the ruptured cells. It is obvious that in most of these somewhat
crude processes, there must be a good deal of more or less waste
residues. These are often worked uj) by distillation, so as to
reduce the loss of oil to a minimum. The distilled oils, however,
as has been indicated above, are of considerably inferior quality
to the expressed oils, and are practically never marketed as such.
They are usually kept separately and used to mix with the cheaper

226

PERFUMER, y:

qualities of the expressed oil. In dealing -with these exi)ressed
oils, it must be remembered that not only must the water be
completely removed from the oil (which is, of course, equally
true for distilled oils), but also the albuminous and similar matter
derived from the fruits, and which never occurs in distilled oils,
must be got rid of completely*, since such impurities tend to
decompose, and impart a very unpleasant odoxir and flavour to
the oil. (Refer also to U.S.A. Patent Specification No. 1353109 ;
and P. c& E. 0. P., 1921, 18.)

The solvent extraction processes may be divided into two
princqDal classes. Of these the older is the extraction by means
of a non-volatile solvent, such as animal fats or vegetable fixed
oils. This method may be subdivided into (a) enfleurage, where
only normal temperatures are employed, and {h) maceration,
where heat is applied. The more recent jirocess of extraction is
that by means of volatile solvents, such as petroleum ether, where
the solvent is diiven off and the extracted perfume material, etc.,
is recovered and marketed in a concentrated form.

The marketed products of enfleurage and maceration are the
well-known pomades and perfumed oils, or, of course, the floral
extracts obtained therefrom by “ washing ” with alcohol. The
method of extracting the perfume from delicate flowers by means
of a non-volatile fatty solvent is of considerable importance, and
is fairly ancient and of very general application in the treatment
of flowers. The method in which the treatment is applied differs
according to whether the odorous constituents of the flowers are
capable of withstanding a more or less elevated temperatmu or
not. And again, it differs according to whether the flower
contains the whole of its potential perfume in a directly available
form, so that the killing of the plant tissues by means of hot fat
is a matter of indifference, or Avhether the perfume exists in the
form of some glucosidal or similar compound, so that as fast as
the fat removes the actually existing perfume material normal life
processes in the flower cause the decomposition of more of the
glucoside uitli liberation of more perfume material. In the latter
case it is obvious that the flower tissues must be kept alive as
long as possible, and hot fat is inadmissible. This point is exempli-
fied in the case of jasmm, the perfume material of which can be
extracted either by volatile solvents or by cold enfleurage. But
both the yield and quality are much superior if the enfleurage
process be adopted. Mviere, following the previous work of
Hesse, gives the following explanation of this important difference

227

15—2

PERFUMERY

{La Parjwnerie Moderne, 1921, 225). It is quite clear that the
jasmin flower contains one or several glucosidal bodies. He has
made exjDerimcnts on the effect of a preliminaiy hydrolysis before
extraction, and in all cases obtained a higher yield when hydrolysis
2Dreceded extraction. It is customary to say that the enfleurage
IDrocess yields four to five limes as much as the direct extraction
until a volatile solvent. But it must be remembered that, when
the enfleurage pomade is washed with alcohol, a considerable
amount of fatty material is dissolved, so that the true perfume
yield by the enfleurage process is not so much higher than that by
the dii’ect extraction b}'’ petroleum ether, as is generally supposed.
But it cannot be denied that the odour of the two products is very
difl'erent. In the enfleurage product the presence of indol is very
noticeable, and this is due to glucosidal decomposition under the
influence of an enzjmie.

Enfleurage and maceration jirocesses consist in placing the
flower in contact with fat (usually high-grade lard or fine beef
suet) or with olive oil, and sometimes mineral oil. It is absolutely
essential that the fat or oil should be of the veiy higliest grade and
as free from fatt}’" acids as possible. The essential oil of the flower
is dissolved out by the fixed oil, wliich eventually absorbs the vdiole
of the perfume material from the plant. The following is, briefly,
the ju’oeess adopted in the maceration of flowers as detailed by
Charabot (“ The Present State of the Perfume Industry ”) : —

The fat being molted on the water bath (or the oil being
heated), the flowers to be treated are added to it, and the mass
is stirred to assist the extraction. The exhausted flowers are
replaced b}'’ fresh ones until the fat is sufficiently charged with
perfume. Eor that purpose a given weight of flowers is allowed
for a charge of fat. The flowers, after treatment, still retam some
of the perfumed fat. This is removed from them by pressing
them, whilst hot, by means of presses. In this way there are
obtained jromades when fats are emplo5’’ed, and perfumed oils
when olive or mineral oils are used. The process is carried out
at Grasse, jDrincipally in the case of the violet, the rose, the orange
flower, and the cassie blossom.

Certain flowers, such as the jasmin and the tuberose, wliich
contain in the free state only a portion of the odorous matters
which they are capable of yielding, must, as indicated above,
be treated bj" the jirocess of cold enfleurage. Eat is spread on
both sides of* a sheet of glass surrounded by a wooden frame. On
the upper surface of this apparatus, which is called a “ chassis,’^

228

PERFU MEE Y

the flowers are spread. Another chassis is placed on the top of
the one thus charged, and so on. The flowers are thus enclosed in
chambers of which the top and the bottom faces are covered with
fat. The fat oh the bottom surface becomes perfumed b}"- contact
and by diffusion ; the odorous matters which escape are retained
by the fat adhei'mg to the upper surface.

After a certain time — tlic next da}' in the case of jasmin — the
exhausted flowers are rei^laced by fresh ones, care being talcen
to turn the chassis over. This operation is repeated until the
desired concentration is obtained. If it be rccpiired to prepare a
perfumed oil instead of fat, the chassis employed differs from that
described above in the fact that the sheet of glass is replaced by a
metal grid which supports a thick cloth winch is saturated with oil.

A\hether the “ maceration ” process or the “ enfleurage ” pro-
cess be emj)loycd, the odorous products are obtained m the form
of pomades or perfumed oils.

The perfume is dissolved in a vehicle, fat or oil, from which it
must be freed. For that purpose use is made of the property,
which the odorous compounds possess, of dissolving in alcohol,
which property is not possessed by the fatty matters employed.
It is suffleient to beat up the pomade with alcohol for the latter
to absorb the perfume without cb'ssolving appreciable quantities
of fat. i\Iorcover, the small proportion of fat retamed by the
alcohol is eliminated by cooling the solution to a temperature
of — 10° to — 15° C. and by subsequent filtration. The exhaustion
of the fats is effected mechanically by means of hatleuses (beating
machines). Several successive washings are necessary.

These alcohol washings form the exlrait-s aux fleurs or floral
extracts of commerce, and the exhausted fat, from which the
greater part of the perfume material has been thus extracted, is
sold as corjjs eimise for use in soap perfumery. The pomades are
themselves sold under numbers, usually multiples of 12 — thus,
flower pomade No. 12, 24, 36, or 72 ; the higher the number
the higher the degree of concentration claimed for the pomade.
In the same way the alcoholic washings knovm as extracts arc
usually sold as triple or quadruple, and are, especially the “ triple ”
extracts, frequently bottled off as handkerchief perfumes as they
come from the manufacturer, or, blended vith other natural or
synthetic perfumes and then marketed under fancy names.

The extraction of perfumes by means of volatile solvents is a
comparatively new industry, although one wliich has recently
made, and is still making, very rapid strides. The process was first

, 229

PERFU MER Y

suggested Robiquet in 1830j when, of. course, light petroleum
ether was unknown in commerce. It u'^as not, however, turned
to industrial account mitil successful experiments were carried out
by Massignon ; but it is pre-eminently to Naudin that the process
has developed into a successful industry on a large scale. To-day
there are more than twenty factories in the south of France alone
which carry on the extraction of flower perfumes by this method.
In 1879 Naudin took out his master patent {No. 130137, French
Patent) on a ' New Commercial Method of extracting Perfumes
in vacuo and in the Cold.” The apparatus therem described con-
sisted essentially of an extractor formed of a closed receptacle
vdth a pannier for holding the flov’^ers, with a decanter and an
evaporator. The extract was charged with the flowers and solvent,
and the cover replaced and sealed. After contact with the flowers
for about a quarter of an hour, that part now charged vdth
perfume was directed b,y means of diminished pressure into the
decanter, where the water from the flowers separates. The
solvent eventually found its way into the evaporator by gravity.
The solvent was then evaporated at the ordinar3^ temperature in
vacuo, so as to avoid all heating efi'ects. The condenser was kept
at a very low temperature by artificial means. As regards solvents,
Naudin suggested ethyl chloride and the lighter fractions of
American petroleum. (Interesting accounts of Naudm’s work
will be found in the Bull. 8oc. CMm., 1882, 38, 586, and in the
Monilcur Scieniifiq^iie, February, 1883, 174.) Naudin established
the validity of his patent in the French Court of Appeal, but the
expenses of the litigation nearly ruined him, and he abandoned
the patent in disgust, and it may be regarded as the substantial
basis of all methods in use to-da}’- in France. The essential oil and
resins of the plant are the onl}^ perfume bearers, and in choosing
a solvent for extraction purposes the following points have to be
carefully borne in mind : —

(1) It must dissolve out the v4iole of the odour-bearing sub-
stances present in the plant.

(2) It must be perfectly neutral and inert and have no chemical
action whatsoever on the odorous substances.

(3) It should dissolve as little else as possible from the plant
tissues.

(4) It must distil steadily within such limits of temperatm-e
that the perfume material is not damaged by the heat necessary
for distillation, and so that the perfume material should not itself
volatilise with the solvent and so cause considerable loss.

230

PERF.U MER 7

(5) It must leave no residue and no odour behind on evapora-
tion.

The principle of extraction 'is more or less that of a Soxhiot
extractor, so that the process is continuous. When the whole of the
perfume is extracted by the sokent— very low boiling petroleum
ether being the most suitable for nearly all purposes— -the solvent
is recovered, and the residue consists of the essential oil, resinous
matter, fat, wax and coloiu-ing matter. This raw material is
usually solid or semi-solid on account of the wax and fat present ;
hence the name “concretes.” But as the wax and fat are
insoluble in alcohol, it is obvious that the emploj^ment of these
concretes gives rise to considerable inconvenience, usuall}- accom-
panied by a loss of alcohol, as perfect filtration is necessary to
separate the insoluble waxy matters. Charabot has worked very
successfully in the direction of removing this inconvenience. He
gives the following brief summary of the outluies of improvements
which lead one from the concretes to the so-called “ absolutes ”
or “ liquid flower oils,” as they are sometimes called (“ The
Present State of the Perfume Industry,” Paris, 1909, p. 8) ;

“ The period at which the process of extraction of perfumes by
volatile solvents entered into the region of industrial realities,
some fifteen years ago, coincided exactly with the time of my first
researches at the Sorbonne, in the laboratory of Charles Friedel,
in the same laboratory where, first under the direction of Wurtz
and subsequently under that of mj’' illustrious and lamented
master, such a strenuous and glorious struggle had been main-
tained for the definite triumph of the splendid atomic theory,
thanks to wliich organic chemistry has produced the marvellous
results vhich are so evident to all. The industiy of the artificial
perfumes, on the morrow of the discovery of ionone, had just
taken a new step in advance, and the sjmthetic jiroducts were
begiiming to claim their place in compositions of the finest quality.
Perfumery then had need of natural raw materials sufficiently
powerful, and consequently sufficiently concentrated, not to be
dominated, crushed out of existence by the chemical perfumes.
These latter were capable of imparting, even to the most delicate
compositions, valuable characters of originality and fixity, but
only on the express condition that they can be sufficiently
dominated by products derived from flowers, which are the only
ones which can impart delicacy and sweetness. It was this
necessity, accentuated still more by the tendency of fashion
towards powerful and tenacious perfumes, which struck me,

231

PEEFU MEET

together with the inconveniences involved by the first products
obtained by means of volatile solvents. And thus my researches
were directed towards the obtaining of the -perfumes of flowers
in the form of products both powerful and soluble in alcohol.
The}'’ soon led to a satisfactor}' solution and the preparation of
products conforming with the desiderata mentioned above.
Since then we have been able to substitute for the first processes
which I invented methods which are more perfect because they
have been deduced from the accumulation of acquired knowledge
both on the composition of the odorous matters and on their
successive states m the plant. And these methods, made appio-
priate to the treatment of each flower, have enabled us, by
employing the solvents m a suitable manner, to leave the vegetable
wax, the inodorous substance which is insoluble in alcohol, beliind,
and to extract solely and completely the odorous principles in the
form of products entirel}' soluble in alcohol. These products, the
absolute fiower oils, are consequently extremely convenient to use,
since it is only necessary to pour them into alcohol to obtain a clear
solution of any concentration that may be desired.

“ But, being extremely powerful products, they have a some-
what high value, and their prices differ from one flower to another.
In order to have for each flov'er products which are comparable
among themselves, and which can be sold at a price which makes
them more convenient to handle, it was most desirable that these
products should be standardised in sirengtli and of uniformly
excellent quality.

” The form of liquid floiver oils is the most advantageous from
all points of view for the utilisation of the odorous products
extracted from plants. In addition to all the quahties enumerated
above, the liquid flower oils possess the very important advantage
of presenting no variation from one crop to another, since they do
not contain, like the solid flower oils, the odourless wax, the
proportion of wliich is essentially variable according to the
season.”

Amongst the flowers which are regularly treated in this manner
may be mentioned rose, orange. Jasmin, tuberose, cassie, jonquil,
narcissus, carnation, mignonette, broom, mimosa, and "violet.

The exact method by which the insoluble wax is removed from
the concretes differs according to the manufacturer, but in general
it consists of agitating the concrete vdth alcohol in suitable
machines {batteuses) and removing the insoluble matter by
filtration, and then cooling the filtrate to 20° below zero in order

232

PEUFUMESY

to cause tlie last traces of dissolved wax to separate. The
“ absolute ” oil is separated either by removing the alcohol m
vact!o or by salting out and separating. Attempts, partially
successful, to remove all colour from these absolutes have been
made by distilling the oil from the absolute. Owing to the intense
strength of these oils, the}' are freciuently standardised vdth a
neutral body so that thc^' are perfectly soluble in alcohol, and
a whole series of absolutes by one maker may have identical
strengths in relation to the finished product in which it is to be
xised.

FACE POWDERS. — ^Toilet powders are merely mixtiires of
certain white powders, tinted or untinted as desired, and per-
fumed to taste. The absolute essentials of a satisfactory’' face
powder are (1) freedom from grittiness, (2) the desned amount
of adherence to the skin, (3) satisfactory colour and perfume.
For the first, the most perfect grinding (where grinding is neces-
. sary) and sifting must be employed, so that the resulting powder
be absolutely impalpable. In order to cause the powder to
adhere to the skin, a careful choice of the main ingredient is
necessary, as well as the discreet employment of small quantities
of a subsidiary substance. For example, wheat starch does not
adliero to the skin nearly so well as does maize starch. The
questions of colour and perfume -are, of course, matters of taste
which do not require discussion here.

The principal constituent of the older-fashioned, and still highly
esteemed, face powders is starch powder, the most usually em-
ployed varieties being maize and rice starch. The old-fashioned
violet powder was essentially a mixture of starch and powdered
orris root with a trace of perfume.

These old-fashioned powders have been to a certain extent
replaced by the more modern “ talc ” or “ talcum ” powders,
which are based on finely powdered talc (q.v.).

To these powders a small quantity of particularly adherent
substances is commonly added, amongst wliicli are zme oxide,
bismuth carbonate, subnitrate and oxychloride, zinc or magnesium
stearates, kaolin, and kieselguhr.

The mineral substances usually incorporated in these powders,
apart from those above mentioned, are precipitated chalk, light
magnesium carbonate, but scarcely baiium sulphate, as is often
stated, except occasionally in very small quantities, as it is so
extremely dense.

233

PEBFU MERY

FormulaB b3^ the hundred for these preparations are to be found
in all the text-books on practical perfumery. (See also P, &
E. 0. B., 1923, 442.)

FAGARA XANTHOXYLOIDES.— See “ Xanthoxylum

Ohs.”

F ARNES AL. — See “ Farnesol.”

FARNESOL. — ^This body is an aliphatic sesquiterpene alcohol,
of the formula CiqHsgO. It occurs in the essential oils of ambrette
seed, acacia (cassie), lime flowers, mignonette, and lilac flowers.
In ambrette seed oil it is present to some extent as the ester of
palmitic and other acids. In order to prepare it from this oil, the
oil should flrst be saponifle’d, after dilution with alcohol, by
heating it with alcohohc potash under a reflux condenser for
eight to ten hours. The alcohol is removed by distillation, and
the residue washed with water. The crude farnesol is distilled in
a current of steam, and purified by conversion into its phthalic
acid ester. It is present in ambrette seeds to the extent of about
0- 1 per cent., associated with a little decylic alcohol. It is a fragrant
oil of apparently very little odour, but in dilute alcoholic solution
it has a sweet odour recalHng that of a mixtine of hly of the valley
and cedarwood oil. ■ It has the following characters : —

Boiling point at 10 mm. . . 160°

Specific gravity .... 0*887

Optical rotation .... 0°

Refractive index . . . .1*4881

The constitution of farnesol has been established by Kirschbaum
{Berichte, 1913, 46, 1732), who has also prepared it synthetically
by acting upon diliydropseudoionone with magnesium bromoacetic
ester. The resulting hydroxydihj’-drofarnesic ester is heated with
acetic anhj^dride and sodium acetate, when farnesic method ether
results, from wliich farnesol is set free. (See also Ruzicka, Helv.
Chim. Act., 1923, 6, 492, for the complete synthesis of farnesol.)

If farnesol be oxidised by chromic acid mixture, the correspond-
ing aldehyde, farnesal C15H24O, results. This is an odorous body
having a specific gravity 0*895, refractive index 1*4995, and
boiling at 174° at 14 mm. It forms a crystalline semicarbazone
melting at 133° to 135°. Farnesol forms an acetic ester, farnesyl
acetate, boiling at 170° at 10 mm. pressure.

Farnesol is of considerable value in perfumery if used with
discretion.

234

PEEFU MEB Y

Ku/iiclva {Joe. cit.) gives the following as the characters of the
specimens of farnesol prepared from the sources quoted : —

Source of farne'Ol. Specific gravity.

Ambrette seed oil . 0-885 at 18° '

Xeroli oil . . 0-803 at 15°

Citronella oil . 0-895

Java cananga oil . 0-895 ,,

Synthetic . . 0-891 at 20°

(7-Nerolidol . . 0-895 at 18°

Eefraotive index.
1-4881
1-4899

1-4890

1-4924 at 18°

It is probable that some of these specimens repi-esent geometrical
isomerides.

Xaef & Co. have patented the preparation of farnesol by the
action of acetic acid upon nerolidol, or bj' the oxidation of
nerolidol to farnesal by means of chromium trioxide and reduction
of the farnesal (International Convention date, March 22nd, 1923).
(See “ Xerolidol.”)

FENCHONE. — ^This ketonic compound, of the formula
C^ioHicO, is found in bitter feimel oil, and also to a small extent in
the oil of Lavandula Sfoecha-s. In both these oils it exists as
dexiro-iencliono, but is also found as Zroro-fenchone in thuja leaf
oil. It is an oil of characteristic sharp odour, having the following
characters : —

Boiling point
Melting point
Specific gravity .
Refractive index
Specific rotation

192°-193°

+ 5° to + 6°

0- 960

1- 4630

about + 70°

By reduction fenchone is converted into fenchyl alcohol, melting
at 45°. Fenclijd alcohol always has an optical rotation opposite
to that of the fenchone from winch it is prepared.

FENCHYL ALCOHOL. — ^The chemistry of fenchyl alcohol
is still in a very unsettled condition, on account of the very similar
characters possessed by bodies which are probably isomeric and
difficult to separate in a state of purity. The naturally occurring
body known as fenchyl alcohol has only been found in the essential
oil from the root wood of Pinus paluslris. Two artificial fenchyl
alcohols have been prepared by Schimmel & Co. {Beport, October,
1898, 49 ; April, 1900, 55, 60) which are described as fenchyl alcohol
and isofenchyl alcohol. They have the following characters : —

renchyl alcohol. Isofenchyl alcohol.
Melting point ... 45° . . 61° to 62°

Boiling point . . . 92° at 11 mm. .. 98° at 13 mm.

, Boiling point of acetic ester . 88° at 10 mm. . . 99° at 14 mm.

235

PERFUMERY

FENNEL OIL. — ^This oil is the product of the distillation
of the fruit of Fcemcxilum vulgax'e, an umhelliferous plant grown
in various parts of Europe, not only for its fruits, but also for its
edible root. It is found in most parts of Europe, being especially
common on the Mediterranean littoral, in Germany, . Moravia,
Galicia, Bukovina, Moldavia, Boumania, France, Italy, and
Macedonia. It is also found freely in Persia, India, and Japan.
Two special types of oils are recognised in commerce, known as
“ sweet ” and “ bitter ” fennel. The sweet fennel oil is the
product of the plant frequently known as Fo&nioulum dulce,
which is, in all probability, only a variety of the ordinary wild
plant. It is also known as Homan fennel. The ordinary wild
bitter fennel, growing chiefly in France, Spain, Algeria, and
Japan, yields the so-called bitter fennel oil.

The yield of ordinary or cidtivated bitter fennel oil depends on
the district from wliich the fruits are collected, varying from
3 to 5*5 per cent. According to Schimmel & Co., the principal
commercial varieties yield the follovdng amounts of essential

on : —

Per cent.

Saxon fennel (Liitzen) . . . 4:-4-5‘5

Galician . . . . . 4-6

Moravian ..... 3

Roumanian . . . . . . 4’6

The distillation residues are of great value as fodder for cattle.
When dried, they contam from 14 to 22 per cent, of proteids, and
12 to IS- 5 per cent, of fat. Normal bitter ferniel oil has the follow-
ing characters : —

Specific gravity . . . 0-965-0-977

Optical rotation . . -j- 11° to -f- 24°

Refractive index . . l-5280-l*53S0

A good quality oil congeals vdthin the limits -|-'5° to -f- 10°.
The oil is soluble in its own volume of 90 per cent, alcohol.

The principal constituent of the oil is anethol, which accounts
for its odour resembling aniseed oil. It is present to the extent of
50 to 60 per cent, in high grade oils. It is also contains fenchone
{q.v.), which is absent from the so-called sweet fennel oil. The
terpenes pinene, camphene, phellandrene and dipentene are also
present, as well as small quantities of methyl-chavicol, anisic
aldehj^de, and anisic acid.

The oil obtained from the sweet or Roman fennel, which is
obtained to the extent of from 2 to 3 per cent, from the seed

236

PERFU MER Y

gro-mi in Southern France, has a high anethol content, and is free
from fenehone. It has a specific gravity 0-976 to 0-980 ; optical
rotation -— 5 ° to + 1G° 30' ; and congealing point -4-10° to
14-5°.

I\Ineedonian fennel oil resembles the French sweet fennel oil.
It has a sweetish taste, due to its high anethol content and its
freedom from fenehone. The yield is from 1-7 to 2-8 per cent.
The oil has a specific gravity 0-970 to 0-980 ; optical rotation
-f 5° to 4-12° ; and congealing point -f- 7° to -f- 12°. Sicilian
fennel oil is distilled -from Fcc7iiGiduni pijici'itian, Icnomi in Sicily
as ass's fennel {Finocchio d’ asino). The fruits are used as a spice
in southern Italy. Thej’’ jneld about 3 per cent, of essential oil,
of specific gravity about 0-950, containing little or no anethol,
as it does not congeal even at — 5°.

The wild growing plants of the bitter fennel, found in France,
Spain and Algiers, jdeld about 4 per cent, of essential oil of
specific gravity 0-905 to 0-925, and optical rotation -j- 40° to
4- 68°. The principal constituent of this wild oil is the terpene
cZc.'ciro-a-pheUandrene. It also probabty contains the compound
di-para-methoxy-stilbene, melting at 214° to 215°.

The Japanese oil is distilled from very small fruits, which
are knovm as J apanese aniseed. The 'oil very closely resembles the
ordinary German oil.

Tard}’’ (“Etude analytique sur quelques essences du genre
anisique,” These, Paris, 1902, p. 23) has examined the oil from
Algerian bitter fennel. It had a specific gravity 0-991 ; and
optical rotation, -f 62°. In it were identified pinene, phellandrene,
fenehone, methyl-chavicol, anethol, a sesquiterpene, and, probably,
thymohydroquinone.

The herb yields an oil which differs from that of the fruits, but
'this oil has not been fullj’- examined. The oil distilled, however,
from the herb Fcsniciihm capillacezim in Java (from the leaves
and stems) was fmmd {Jaarh. dep. Land. Ned. Ind. Batavia, 1907,
45) to have a specific gravity 0-970 ; optical rotation, 4- 40°50' ;
and congealing point, 12-8°. Anethol and methyl-chavicol are
present in the oil.

The fruits of the water fennel Oenanthe Pliellandrium yield
from 1 to 2-5 per cent, of essential oil. This has a powerful and
penetrating odour, and has the following characteristics : specific
gravity, 0-850 to 0-890 ; optical rotation, -f 12° to 4-19° ; refrac-
tive index, 1-4840 to 1-4950. It consists very largely of the
terpene phellandrene. It also contains an aldehyde 0^ H^gO

237

PERFUMER Y

which has been named phellandral ; an alcohol Ojq H 20 0, termed
androlj and an alcohol of unknown constitution.

Sage and Goodale (P. c& E. 0. R., 1922, 18) have examined a
Spanish fennel oh, the yield being 3*75 per cent.

The oil has a sweet taste and good flavour, and possesses the

following characters : —

Speciflc gravity at 16'5° . . . 0-9638

SiDecific gravity at 25-0° . . . 0-9571

Refractive index at 25-0° . . . 1-5243

Optical rotation at 20-0° . . . + 17-8°

Solubflity in 80 per cent, alcohol . 1 in 5

Congealing point . . . . — 3-5°

By fractionally distiUing the oil, under ordinary atmospheric
pressure, they obtained the following yields : —

3?cr CGiit*

Distniing between 180° and 200 ° . . 7 *

., 202° „ 210° . . 18

„ „ 210° 225° . . 57

,, ,, 225° ,, 235° . . .15

above 235° ... 3

The low congealing point of the entire oil shows that it contams
a low proportion of anethol, but the fraction distilling between
225° and 235° was found to have a congealing point of 13-3°, and
the separated solid was undoubtedly anethol.

They attempted the oximation of the oil and of the low^er
boiling fractions, but found practically no ketone present, and
the yields being under 2 per cent, indicate the absence of notable
proportions of fenchone. The oil yielded reactions indicating
the presence of some pheUandrene, but the proportion must have
been quite low.

It is apparent from these experiments that these fruits, as
grown in Spain, do not yield an oil containmg anj’- notable pro-
portion of fenchone, and that the amornit of anethol cannot be
considered sufficiently high to make the oil as good for. medicinal
purposes as oil from Saxon or Galician feimel.

FERULA SUMBUL, OIL OF.— See “ Sumbul Oil.”

FEVERFEW OIL. — ^The oil of Pyretlimm farthenium is
distilled on a small scale. It contains a terpene, borneol, and
bornyl esters. Its specific gravity is from 0-900 to 0-960.

fixatives. — ^T he question of the lasting power of perfumes
is one which is of the highest importance to the perfumer to-day,
as the general tendency has grown to requiring perfumes which

238

PERFU MEB T

shall be lasting and tenacious, a s differentiated from t hose which,
h owcTcr sweet, votatilise very rapid ly. To-day it is necessary
to recogniso'tTiat tliere are two ver^harply differentiated classes
of fixatives. There are, in the first place, those which are so
nearl}- odourless, either se or on account of the minute
quantities necessary in jwactice, and so act almost entii-ely as
j)ure fixatives only : and, in the second place, there are those
powerful fixatives which are also highlj' o doro us themselves, so
that they modify the odour of the other~ consl^uents of the
perfume to a more or less noticeable extent, and to that extent
become active odom* bearers in the perfume itself, as well as mere
fixatives. At one end of this series there are, of course, those
whose contribution to the odour is but slight, and again, at the
other end of the series, those that definitpl}’’ contribute to the
odour in such a way that, as the more Volatile constituents
evaporate, the odour of the ” fixative ” becomes more pronounced.

It has been said that the ideal fixative is one which will equalise
the differing rates of evaporation of the various odorous con-
stituents of the perfume. This, however, is scientifically quite
inacciu:ate, as the alteration in the vapour tension of one liquid,
when mixed with another liquid of different vapour tension, is a
mathematical matter depending on the individual liquids them-
selves. 3?or example, if bergamot oil, neroli oil, and lavender oil in
an eau de Cologne would (to put it in popular form) evaporate in
A, B and C hours respectively, the addition of a given fixative will
cause the evaporation periods to become A -f- X, B -f- X^, and
C -b X2 respectively, where X, X^ and X^ may be different, and
in general A -f.X, B -f- X^, and C -b X^ wiU almost certainly be
different. The real effect ^vill have been a general prolongation
of the whole of the perfume, which mil, during the evaporation
period, gradually change in nature according to the loss of any
given constituent. The gradual development of the public taste
in favour of tenacious perfumes has led to the manufacture of
numerous artificial fixatives, and to-day it is correct to say that
hardly any perfume formula can be considered complete mthout
its ipcluding a recognised fix ative. Fixatives may broadly be
classified as follows : —

(1) Pure fixatives, which do little else than render the perfume
-less fugitive.

(2) Fixatives having a pleasant odour, which modify the
perfume itself in a noticeable (more or less) degree.

(3) Fixatives having a disagreeable odour, which are used in

239

PEEF U 3IEE T

minute quantity and Avliicli, in the very dilute solution in which
they are used, heconie insensibly agreeable, like “ garlic smeared
round the salad bowl.”

Deodorisation of alcohol is, of course, a misnomer in regard to
-fixation. The use of any ordinary fixative on an alcohol wliich
has an undesuable odour merely acts as a cover, and does not in
any way destroy the bad odour. In fact, it is no exaggeration to
say that more rubbish has been VTitten in regard to the question
of fixatives than in most branches of practical perfumer}^'. No
fixative wiU “ overcome ” the effects of S 3 mthetics. The truth i^s
that these “ effects ” do not require overcomi ng. If the perfumer
wants a perfume of overpowering strength, as certain classes
demand, he vdtl use an excess of synthetic s and get his powerful
odour . If he does not want this, he vdll use minute quantities
of S 5 Tithetics which do not, when properly used, produce any
result which requires the words “ harsh ” or “ chemical ” to'
describe it. Fixatives do not enter into this question at aU.

The classes of fixatives given above are recruited from three
main sources : (1) animal substances ; (2) vegetable oils, resins
and balsams ; (3) artificial or synthetic compounds.

Fixatives derived from animal sources have long been held in
high esteem by perfumers. The bodies employed for this pm-pose
are musk, ambergris, civet, and castor . It has been seriously
suggested that the popular use of these animal perfumes was
initial^ due to what the French have named ‘ Vodeur de chair'
and that the animal perfume had a sex attraction. This suggestion
vdll hardly bear examination. There is no doubt that the four
main animal fixatives do fix the perfume exceeding^ well and,
when used vith discretion, do not interfere with the main floral
odour when such is being used. For example, the highly disagree-
able civet, wliich in the natural state has a foul faecal odour, is
used in the finest wliite rose perfumes manufactured, and at no
stage of the evaporation of the perfume does any disagreeable
civet odour become apparent.

The principal natural vegetable fixatives are the balsams, gum -
resi ns, and veiy high-boiling essential oils whose constituents are,
very frequentty, sesquiterpenes and sesquiterpene alcohols.
Amongst artificial substances used as fixatives there are a number
which are practicallj’’ only fixatives, although they may be used
as solvents as well, for example, benzyl benzoa te, with its high
boiling point and its useful solvent action on artiBcial musk ;
and there are a* number which have very marked odours as well

240

PERFUMER Y

as fixative properties. Por example( ^diphenyl oxide ^ sometimes
referred to as a fixative. In fact, it Is a high-boiling substance
'svith a powerful geranium odour, and is more correctly described
as an artificial geranium perfume of great las ting power. For an
exhaustive list of substances classed as fixatives, but which
^ should be examined carcfuUy in regard to the real proportion
between odour value, reference may be made to the following
works : Durvelle, “ The Preparation of Perfumes and Cosmetics ”

I (London : Scott, Greenwood & Co.), 1923, pp. 124r-126 ; and
Poucher, “ Perfumes and Cosmetics ” (London : Chapman and
Hall), 1923, pp. 201-203.

FLEABANE OIL. — ^The fresh flowering herb Erigeron cana-
densis jdelds about 0-5 per cent, of an aromatic essential oil known
as fleabane oil. It contains limonene, terpineol, and traces of
citronellal, and has a specific gravity 0-855 to 0-870 ; optical
rotation, -f- 52° to -}- 81° ; acid value, 0-15 ; and ester value, 34
to 109.

FLORIDA WATER. — ^This perfume, which, of course, is not
protected with a proprietary name, is one of exceedingly popular
character in America, and, to a smaller extent, in far Eastern
countries that import it. It is, in the United States, largely what
lavender water is in England. It is a toilet perfume somewhat
resembling a mixture of lavender water and eau de Cologne,
rounded off with one or more of the following bodies ; cassia oil
(or cinnamon oil, or cinnamic aldehyde) ; elove oil (or pimento
oil, bay oil, or eugenol) ; and lemongrass oil.

FOIN-COUPE. — ^This popular type of perfume is supposed
to reproduce the odour of new-mown hay. It is invariably based
on coumarin, modified by lavender, bergamot, and other perfumes,
according to the exact note the perfumer wishes to give to his
product. The odour of true new-mown hay is due more to the
sweet-scented grass known as Anihoxantlmm odoraium than to
any other grass, although many others contribute to it. Several
different types of clover, of course, also add to the fragrance of the
hayfield odour. This odour is probably the result of glucosidal
decomposition of constituents present in the plants, resulting in
the formation of a little coumarin. (See Anxctican Perfttmer, 1922,
57.)

FORMYLATION. — See “Alcohols, Determination of.”

FRACTIONAL SAPONIFICATION. — See “ Esters, Arti-
ficial.”

241

PERF U MER Y

FRAGAROL.— See “ ^-Naplitliol-butyl Ether.”

FRANGIPANI.— (See also “ Plumiera.” )— This name is
applied to a particular tj^pe of fancy perfume which, at one time,
achieved great popularit}'' in this country. The name is said to
have been derived from the office held by an old Roman family,
namely, of breaking the bread (the meaning of the word) in the
celebration of holy communion. A descendant of this family,
which appears to have adopted the official title into its name,
is said to have introduced a special perfume for gloves wdiich is,
at least by legend, the lineal ancestor of the modern “ Frangi-
pani ” (see below). The name was, at all events, given by
French colonists in the West Indies to the odorous plants Phimiera
nibra and Plumiera alba. These trees belong to the natural order
Apocynaceoi. They are natives of Peru and other parts of South
America, and are found in several of the West Indian islands.
The genus was named bj’^ Tommefort in honom’ of Charles Plumier,
a Franciscan traveller in South America and author of several
works on botany. Phimiera rubra is called b}^ the French in the
West Indies Frangipanie rouge, and also “ red jasmin.” It is a
tree from 12 to 20 feet in height, yielding highty odorous flowers,
which are used b}^ the native women to perfume their linen as
we use lavender flowers. Several other varieties are cultivated,
and are highl}^ odorous. Amongst them is Phimiera acutifolia, a
plant which is cultivated in cemeteries in the Philippine Islands.
The flowers have a marked “ frangipani ” odour, but no essential
oil has been obtained from them. Racon [Philip. Jour. Science,
1909, 4, A, 131) showed that if the flowers be heated to 40° the
odour was destro 3 ’'ed. An extract was obtained by' means of
petroleum ether with the t 5 ''pical odour of frangipani, although
no essential oil could be obtamed.

But the flowers of Phimiera aciiiifolia exhale a very pleasant
and highly esteemed perfume. Descourtilz, in his “ Flora of the
Antilles,” praises with voluble enthusiasm this “ sweet odour,”
comparable, he saj^s, with that of the tuberose or gardenia, and

much in demand by the young girls on fete-days.” The creoles
place the freshly gathered flowers of the frangipani in their
linen and in them rooms, and the planters, to honom’ them guests,
often strew the beds with these blossoms. This very penetrating
perfume still persists for a fairly long time after the flower has
been separated from the tree on which it grew. It was doubtless
in imitation of this that boquets a la frangipane were formerly
compounded.

242

PEBFUMERl

Thi=; species cultivated in India, but its origin is Centi-al
America, probably somewhere about [Mexico. It is not indige-
nous in tropical Asia, as A. de Candolle believed. In India the
flowers are laid in the temples and on the graves, as offerings,
Li the Philippines, t\\o Plumiera is frequently used as a “ cemetery
tree " ; they plant slips which take root easih' and grow rapidly.

The following interesting account of this perfume is due to
Daniel Hanbury and was written in 1S.50, and is abstracted in the
Pcrpnncrij avd Esscntlnl Oil Record (1915, 238) as follows : —

Frangipani is the name of a ver}' ancient, aristocratic Roman
famil}' dating from the eleventh centuiy, a member of which,
Ceucio Frangipani, became a leader of the Ghibcline faction against
the Guelphs during the century following, and man}- times since
then has the family figured in the romantic histor 3 "of Italjx On
board the Santa 3Iaria with Columbus was one Jlercutio Frangi-
pani, and in the Papal army assisting the French King Charles IX.
against the Huguenots was a Mutio Frangipani. The grandson of
the latter was the IMarquis Frangipani, iffarechal des Armees of
Louis XIII., and he it was who turned his ingenuity to a very
unmilitary invention, a method of perfuming gloves, which when
so scented Averc known as ” Frangipani gloves.’’ The authority
is Menage, in liLs ” Origini della Lingua Italiana,” published ait
Geneva in 1GS5 ; he saj^s “ Da uno di que Signori Frangipani
(rabbiani veduto qui in Parigi) fiirono chiamati certi guanti
profumati, Guanti di Frangq^ni ” [from one of which Frangipani
(I saAv him here in Paris) Avere named certain perfumed gloves,
“ Frangipani gloves ”J. From another old record, Le Laboureur's
“ ]\Iemoh-es de Castelnau,” wo learn that a brother of the Marquis
was also associated with the invention : “ Ce dernier JIarquis
Frangipani, et son frere mort auparavant lu 3 ’-, inventcrent la
composition du parfura et des odeurs qui retiennent encore Ic nom
de Frangipane.”

In an extraordinary AA'ork entitled “ Frangipani’s Ring : an
Event in the Life of Henry Thode,” translated from the German
and published in London by Jolm Macqueen in 1904, reference is
made to a AA'ork entitled “ Chronicle of the Island of Veglia and
of the Frangipani Family upon this Island,” by Antonio Vinci-
guerra, Secretar 3 ’- of the Senate and the Republic of Venice, a
Avork mentioned in the Catalogue of Manuscripts in St. Llark’s
Library in Venice. Thode, attempting to trace the origin of the
family, Avrites of it as follows : — -

“ A stalwart race, inliabiting strong castles in Croatia, Avith its

243

16—5

PEBFU MERY

ancestral seat in Modi-usa and Segna (Zengg), which was given
it in fief hy Bela III. in 1260. Driven about by their passions
througli the following centuries to ambitious scheming, wild
undertaldngs, and outrageously violent deeds ; forced by their
tcrrifyuig superstitions to take refuge in fantastic religious
devotions ; heroic and faithless, um’uly and calculating in capricious
change, thej’- wasted their turbulent lives in warring with their
neighbom’S and with themselves.

“ Whence the race original^ came cannot now, with any
certainty, be stated. One authority contends that its home from
the first was in Croatia, and that the name, literally ‘ Frankopan,’
means ‘ Francis the Lord ’ ; others assert that it was a severed
branch of the Roman famity of the Frangipani, whose annals
are stained "with the dastardly betrayal of the last Konradin of
Hohenstaufen bj'' the Lord of Asturia, John Frangipani, and
vith the treacherous assassination of Duke Frederick the Warrior.
Contrary to tliis, the authors of the Venetian genealogies, and
among them the earliest, so far as I Icnow, Francesco Venier and
Zancarola, relate in their chronicle (now in St.’ hlark’s Library)
that in former times a family of the Frangipani came from
Ravenna to Venice, where they became members of the Great
Council, and that, with the death of Giovanni, who held a position
in the hlint, this line became extinct in 1347 ; they also hold
that from these Ravenese-Venetian Frangipanis the Croatian
braneh originally sprang.”

It vdU be noted that the Italian writers mention only per-
fumed gloves, whereas La Laboureur speaks of “la composition
du parfum et des odeurs,” which would appear to include some
essence, powder or pomade. This much is certain, however, that
certain compositions as ^mnade, essence and powder, styled
Frangipani or Frangiptane, were sold by perfumers dorni to a
century ago, when they appear to have fallen into disuse. A
revival of certain peilumes bearing the name occurred in the
’fifties, and formulas apj)eared in Piesse’s “ Art of Perfumeiy,”
London, 1S56, and Celnart’s “ Nouveau Manuel Complet du
Parfumeur,” Paris, 1854. The various formulas to be found vary
so much among themselves that, obvionslj’’, they camiot all
represent the original. “ Pharmaceutical Formulas ” (MacEwan,
1914) gives tlnee such recipes from which to choose, and judging
from their constituents one might describe them as dainty, rich,
and heavy respectivety, according to the predominance of floral
extracts, otto of rose, sandalwood, civet, ambergris, and musk.

244

P ERF U M ERY

It may be taken for granted that the basic odour of *• frangi-
pani ■’ perfumes to-day is that of jasmin, modified with substances
having hea.vy odours.’’

FRANKINCENSE.— Sec “ Boswellia Resin.”

FUMIGATING PASTILLES.— Fumigating pastiUes are
usuaiiv moulded into the shape of cones, and are prepared from
pastes from which the water is driven off after the pastilles have
been cut into shape bj* approju’iate moiilds. These pastes are
made up from selected varieties of charcoal, with potassium
nitrate to ensure even and continuous burning, and mixed aromatic
gums and balsams, Avith other aromatic volatile substances to ghm
a highly aromatic odour on buming. They are. in fact, little else
than “ moulded incense.’’ Frecpicntly a little powdered cas-
carilla bark or other substance burning with an aromatic odour,
is added. Benzoin and storax are the usual balsamic substances
employed, and powdered cascarilla, cinnamon, cloves, cedar
wood and vetivert root are the usual vegetable poAA'ders used.
'V^anillin, heliotropin, and the oils of cedarAvood and sandahvood
are the usual perfume additives. Charcoal is usualty present to
the extent of 25 to 50 per cent., and potassium nitrate from
5 to 7'5 per cent. Occasionallj’^ the charcoal is replaced b}’' red
sandalAA'ood, the pastilles being red instead of black in colour ;
or by fine white pine saAvdust, Avhen the pastilles are nearly Avliite.
The exact formula} for the finest odours are, of course, trade
secrets.

FUSANUS SPICATUS, OIL OF.— The so-caUed Western
Australian sandalwood oil is the distillate of the Avood of Ftisanus
spicatus, a tree originally knoAAm as Santalum cygnonim. The
oil resembles true sandahvood oil in odour, and contains similar,
but not identical, constituents. It is of very great value to the
perfumer, and is largely employed for perfuming soap. The
natural oil has the folloAAing characters : —

Specific graAdty . . . 0-957 to 0-972

Optical rotation . . . 1° to — 8°

Refractive index . . . 1-5015 to 1-5100

Total alcohols (as CigHo^O) . 65 to 78 per cent.

The oil is, however, fractionated so as to contain up to 95 per-
cent. of alcohols, and is obtainable in this condition on the
market.

It has recently been fully investigated by Sanjiva Rao and
Sudborough {Journal of the Indian Institute of Science, vol.'v., xii.,

246

PEBFTJ ME B.y

1923, 163). Tliese authorities give the following account of the
tree, its wood, and the essential oil : —

The sandalwood, although only a tree or shrub, is an important
factor in the timber industry of Western Australia. The species
is somewhat peculiar in its appearance, and certainly has more of
the character of a largo bush than of a tree proper. It has alow,
depressed habit, and is consequent^ decidedly" branchy and
heavily topped. It is seldom more than 8 inches in diameter and
12 to 18 feet high, with stems 8 to 10 feet long.

The value of the wood exported from Australia is given as
£96,050 in 1882, when the price was £10 per ton, and £117,072 in
1918-19, when the price of v/ood was £13 per ton. Most of the
wood finds its way to China and, to a small extent, to other Eastern
countries. Within recent 3 ’-ears increasing quantities of wood have
been imioorted into India as shown b}’’ the following figures : —

Tear. . . . 19M-15 1916-17 1917-18 1918-19 1920-21

' 10 months

Value of imported wood .£8,372 £11,080 £16,080 £29,860 £30,370

The jfield of oil from the w'ood is 2 to 3 per cent, as compared
with a jdeld of 5 to 6 per cent, for the genuine East Indian sandal-
wood {Savialmn album). The oil was first distilled in 1875 by
Messrs. Schimmel & Co., of Leipzig, and subsequent^ the distilla-
tion was undertaken in Fremantle. [And also near Albanj^, -where
a distillery existed in 1900. (E. J. P.).] In 1918-19 3,720 lb. of
oil were distilled in Austraha, and found a market in Australia
and Java as a substitute for East Indian sandalwood oil in both
perfumery and medicine.

The following are the values obtained on the anatysis of fom’
samples of the natural oil : —

Specific gravity at 15/15°

0-957

0-970

0-958

0-972

Refractive index at 25° .

1-5019

1-5040

1-5030

1-510

Optical rotation at 25° .
Solubility in six parts of 70 per

— 7-7°

— 0-7°

— 0-25°

— 0-87°

cent, (by volume) alcohol at
20° ,

Insoluble

Total alcohols calculated as

santalol, CigHo 40

Esters calculated as santalyl

80-0

69-3

76-3

78-5

acetate

2-4

6-5

2-3

3-8

Acid value .

5-0

2-9

4-2

24G

PERFU 2t E R r

A sample of oil B was distilled under atmospheric pressure, and
throe fractions collected and examined ; the following values were
obtained : —

No. of
fraction.

roiling point.

Weiglii in
grams.

rcrccnfage

eight.

O-D i

Optical rota-
tion at 25°.

258-280°

3-2

21-3

1-4994 j

t - 2-0

280-285°

3-1

20-0

1-5014

, -

285-309°

7-0

4G-6

1-5079

+ 1-2

During the distillation, fumes and an emp 5 Teumatic odour were
observed, indicating partial decomposition.

Two hundred grams of the original oil were saponified with
alcohohc potash, washed, dried with anhydrous potassium
carbonate, and subjected to fractional distillation under a pressure
of 9 to 10 mm., using a pear-shaped fractionating column ■with
five pears.

From 180 grams of saponified oil, seventeen fractions and a
residue were obtained, and the analytical data for these fractions
were as follows : —

No, of !
fraction,
. !

Pressure :
in mm.

Temp, in
decrees

Weight

grams.

Optical i
rotation
at 25°. j

Refrac-

tive

index at
25^

Soluble in

C vol‘3. of

70 per cent. |
alcoliol.

Alcohol

^15^24^

per

cent.

- 1

135-150

6-4

— 4-8

1-4942

Insoluble

150-153

9-4

— 4-6

1-4963

—

153-158

10-5

— 4-2

1-5001

—

4 i

153-158

8-6

— 3-6

1-5000

—

158-160

6-5

— 3-5

1-5006

—

6 i

1G0-1G4

5-1

-2-6

1-5004

—

f 1

160-1G4

12-1

. -1-6

1-5022

Clear at 60°

—

9-10

164-166

8-9

— 1-3

1-5034

„ 45°

73*3

• 9

9-10

164-166

6-4

— 1-1

1-5041

» 35°

—

9-10

164-166

10-3

— 1-0

1-5048

„ 26°

—

9-10

166-168

8-4

— 0-9

1-5059

„ 20°

—

9-10

166-168

7-1

-0-6

1-5065

.. 14°

—

- 13

9-10

166-168

8-2

-0-3

1-5067

„ 13°

87-9

9-10

166-168

6-5

+ 0-3

1-5092

„ 6°

—

9-10

168-172

6-6

+ 1-5

1-5101

„ 2°

95-1

9-10

168-172

7-0

+ 1-6

1-5103

» 3°

—

9-10

168-172

22-2

+ 1-4

1-5096

- 28°

87-9

Eesidue

—

25-2

—

247

PERF UMEBY

It was found that the oil contained two isonieric sesquiterpene
alcohols, to which the name fusanol has been applied. The
characters of these alcohols are here compared with those of the
isomeric santalols from true sandalwood oil : —

ft-Fusanol,

1 j3-Fusanol,

a-San-
! talol.

iS-San-

talol,

Boiling point at 6 mm. .

146-148°

153-155°

158°

16°

“l5°

0-9775

0-9753

0-979

0-973

25°

. .

1-6060

1-5100

1-4968

1-5067

25°

+ 5-7°

+ 2-6°

+ 1-1° 1

— 42°

Molcular weight found .

213

217

• 215

—

Molecular refraction
Temperature at which mixture
of 6 '5 parts by volume of 60

67-39

67-91

65-88

..... 1

67-48

per cent, (by weight) alcohol
and one part by volume of
oil becomes clear

. 5-6°

4°

12° ;

9°

The results of this important investigation are summarised as
foUows : —

( 1 ) The so-called West Australian sandalwood oil is derived
from a species of tree quite different from the Sanialum album,
Linn., the species from which the East Indian oil is obtained. It
differs in general properties from the East Indian oil and, in order
to avoid confusion, it should be given a name other than sandal-
wood oil.

( 2 ) The oil, as distilled direct from the wood, differs in most of
its .analytical data from the genuine sandalwood oil. It does not
fall within the limits allowed by the British Pharmacopoeia as
regards specific gravity, optical rotation, alcohol content, or
solubility in 70 per cent, (by volume) alcohol at 20°.

( 3 ) By fractional distillation and removal of the lower boilmg
sesquiterpene fraction it is possible to obtain an oil which passes
the B.P. tests for genuine sandalwood oil, vdth the exception of
the optical rotation, which is always well below the standard,
required by the B.P.

(4) Although it is easy by fractional distillation to obtain an
oil containing more than 90 per cent, of alcohols (calculated as
C 15 II 24 O), nevertheless the alcohols present are not identical with

248

PEBFU MERY

either of the two santalols present in East Indian oil, but are
isomeric "with them.

(5) There appear to be at least two alcohols present in the
West Australian oil. They are probably to be represented as
C15H25O, and, in order to distinguish them from the isomeric
santalols, they have been termed a- and /S-fusanols.

(G) These fusanols jdeld hydrogen phthalatcs and phenyl-
urethanes. The fact that they react much more slowh' than the
santalols with phthalie anhydride indicates that they are probably
secondary, and not primary, alcohols.

(7) From their molecular refractions it is probable that both
fusanols are bicyclic compounds containing two olefine linkings.

(8) The statement that during distillation of the oil under
reduced pressure there is a loss of alcohols has not been confirmed ;
neither steam distillation nor distillation under reduced pressure
appears to change the alcohol content.

(9) It is generally agreed that for perfumery purposes the West
Australian oil is inferior to genuine sandalwood oil.

The witer (E. J. P.) does not agree vuth conclusion No. 3.
Fractionation usually results in oils with a specific gravity below
that of the true sandalwood oil, but the correct optical rotation
can be attained.

GALANGAL OIL.— Galangal oil is used as a flavouring
material rather than as a perfume. It is obtained by the distilla-
tion of the rliizome of Alpinia officinarum, a plant cultivated in
Cliina and Siam. The oil has a specific gravity 0-910 to 0-928,
optical rotation, — 1° to — 8° ; and refractive index from 1-4760
to 1-4850. It contains terpenes, cineol, and oxygenated con-
stituents not yet identified.

GALBANUM. — ^This body is a gum-resin obtained from
several species of Pcucedaivum, principally Peucedaimm galhani-
fiormn, belonging to the natural order Umbclliferce. It contains
from 8 to 10 per cent., sometimes as much as 24 per cent., of
essential oil of sharp aromatic odour. It is used to a small extent
as an odorous fixative. The essential oil has the following
characters : —

Specific gravity . . . 0-905-0-955

' Optical rotation . . . — 10° to -}- 20°

Refractive index . . . 1-4840-1-4960

It contains pinene, myreene, a sesquiterpene (cadinene ?), and

249

PERF U M E B 7

a sesquiterpene alcohol, CigHocO, which has been termed cadinol.
Five samples of the gum resin itself examined by Beckirrts and
Bruche had the following characters : —

Specific gravity

1-11

1-13

1-109

1-133

1-121

Ash, per cent.

4-0

8-7

4-1

8-4-

4-9

Resm, per cent.

; 68

Acid value of resin

i 40

Ester value of resin .

GARDENIA. — ^Thc gardenia is a highly odorous flower, several
species of which are cultivated, and whose perfume is highly
esteemed. The perfume is rarely extracted from the flower,
most of the boquets knovm by the name being entflely artificial
productions. The most common of the plants cultivated is
Gardenia fiorida, also knovm as Cape jessamine ; Gardenia grandi-
flora is another well-knoum plant. They belong to the natural
order Biibiacece. The plants are indigenous to tropical Asia and
Africa, and also the Cape of Good Hope. In Bengal the plant is
knovm as Gumdlmraja : and in China, where its flowers are used
for the perfuming of tea, it is called Pah-seyna-lma. The flowers
from mixed cultivated species jneld, on maceration vdth hydro-
carbon oil and distillation of the extract, 0-0704 per cent, of an "
essential oil of specific gravity 1-009, and optical rotation 1-47°.
At 760 mm. pressure it commences to distil at 204° vdth partial
decomposition. According to Barone {Boll. Glihn. Farm., 1902,
41, 489), it contains benzyl acetate, the acetic ester of methyl-
phenyl-carbinol, linalyl acetate, methyl anthranilate, and
terpineol.

The artificial perfume is built up on this composition, vith the
addition of various other synthetics, such as benzyl acetate,
phenyl-ethyl aldehyde, and geraniol and its esters. (See also
“ Phenyl-ethyl Alcohol ” and " Gardeniol.”)

GARDENIOL. — ^This is a fancy name given to the acetic
ester of phenyl-methyl carbinol, an isomer of iflienjd-ethyl
alcohol. (See “ Plienyl-ethjd Alcohol ” and “ Gardenia.”)

GAULTHERIA OIL. — See “ Bhch (Sweet), Ofl. of.”

GENET. — See under ” Broom.” -

GERAN ALDEHYDE. — ^This is an alternative name for the
aldehyde citral CjoHieO [g.v.).

250

PERFUMER. Y

GERANIOL. — Geraniol is one of the very important sub-
stances in the perfume industiy. It is found in numerous essential
oilS; both in the form of esters, of which the principal is geranyl
acetate {q.v.), and in the free state. For example, palmarosa oil
contains SO per cent, or more of free geraniol ; citronella oil
contains a considerable amount j all forms of geranium oil
contain much geraniol in the form of esters, and a certain amount
in the free state ; and it is an important constituent of otto of
rose.

Geraniol is not manufactured synthetically, hut is extracted
without anj^ great trouble from oils wliich are rich in it, so that
it is a regular commercial article, and is used to a large extent in
the compounding of artificial perfumes.

Geraniol is a colourless, sweet smelhng oil, having a rose-hke
odour. Its formula is CioHi^OH, so that it is isomeric with
nerol and with linalol. Its characters are as follows : —

Specific gravity . . . 0-880-0-883

Optical rotation ... 0°

Refractive index . . . 1-4766-1-4786

Boiling point. . . . 228°-230°

It can be separated from those oils which contain an appreciable
amount of it, by first concentrating it in the appropriate fraction
uiider reduced pressure, and then mixing the fraction intimately
with an equal weight of absolutely dry powdered calcium chloride,
and allowing the mixture to stand in a desiccator for sixteen
hours at a temperature, of about — 5°. The pasty mass is then
rubbed down with dry petroleum ether, and the liquid portion
removed from the solid portion by means of a suction filter.
After washing with more petroleum ether, the solid compound of
geraniol vdth calcium chloride is treated with water, which
decomposes the compound, with the hberation of the geraniol,
and the oil is purified by fractional distillation. The geraniol
distfis over at 228° to 230°. To prepare it in a state of absolute
purity it should be treated with sodium, and then dry ether and
phthalic anhydride added. The geraniol sodium phthalate is
hydrolysed by alcoholic solution of caustic potash, and the pure
geraniol precipitated by the addition of water.

Rlatau and Labbe effect the separation of geraniol and
citronellol, which often occur together, in the foUovdng manner.
The oil, first' saponified, in order to decompose esters present, is
fractionally distilled in vacuo. The fraction distilling at 120° to
140° at 30 mm. pressure, is heated with its own weight of phthalic

261

> PERFU MERY

anhydride and its own volume of benzene. The niixture is
dissolved in a solution of sodium carbonate, the solution extracted
with ether, and the acid phthalic esters of geraniol and citronellol
liberated by the addition of hydrochloric acid. These esters are
dissolved in petroleum ether, and the solution cooled to — 6°.
Under these conditions, the acid ester of geraniol separates out
in the crj^stalline condition, whilst that of citronellol remains in
solution. The esters, on saponification, yield the corresponding
alcohols in a state of comparative purity. The geraniol ester
melts at about 47°, and forms a silver salt which melts at about
139°.

Geraniol is characterised by its yielding a compound with
calcium cliloride, as above described, and by the formation of a
phenylurethane melting at 82°. On oxidation geraniol is con-
verted into its aldehyde, citral (q.v.).

Semmler and Schossberger {Berichic, 44, 991) have prepared
an isomeric geraniol, which they have named isogeraniol. Geraniol
can be, as just mentioned, oxidised to citral. If citral be heated
with acetic anlij^dride, an alteration in its constitution takes
place by the migration of a CHo group. The citral is “ cnoUsedP
The resulting omZ-citral is reduced by means of sodium amalgam
and alcohol, when the isomeric alcohol is obtained. Isogeraniol is
an oil having a pleasant odour of roses, and possesses the following
characters : —

Boiling point at 9 mm. . . 102°-103°

Specific gravity at 20° . . 0'S787

Befractive index . . . 1-4732

For the estimation of geraniol, see under “ Alcohols, Deter-
mination of.”

The following method for obtaining geraniol commerciall3'' is
given b}’’ Lewinsohn (P. <9 E. 0. R., 1924, 282) : —

Java citroneDa oil is worked up cliiefly for its geraniol, but this
can onty be produced economically if the citronellal obtained
at the same time is further worked up for d-citronellol. It
is, moreover, advantageous to separate from the residues the
sesquiterpene compounds they contain, as thej’- have very
valuable fixative properties and find application in numerous
compositions.

Thirty kilos of Java citronella oil are placed in a copper distilla-
tion vessel, to which is attached a copper fractionating column
about 6 cm. in diameter and 120 to 140 cm. high, filled with glass

262

PERFUMERl

bends or, better, \ntli Rascheg rings, the vessel being heated by
direct gas flame. The exit-tube of the column is connected vdth a
copper spiral immersed in an iron tank of cold v'ater and leading
to a large vacuum flask which serves as a receiver. A stop-cock
between condenser and receiver enables the latter to be changed
wliile maintaining the vacuum in the distillation vessel. It is
useful also to modify this arrangement, so that two receivers can
be employed.

For the first distillation of the oil a not too liigh vacuum — saj’-,
about 10 mm. — is most suitable. The “ crude first runnings ” are
the liquid distilling below 95° at 10 mm., thus ensuring the absence
in the next fraction of anything boiling below the boiling point of
citronellal. The second fraction, from 95° to 110°, is called
“ crude citronellal.” These two fractions must be distilled slowly
to avoid overheating, but after 111° distillation may take place
more rapidly, since only httle citronellal will appear in the “ crude
geraniol ” now collected. The heating is discontinued at 130°,
and the residue in the distillation vessel is transferred to an
enamelled container, where the residues from several operations
are later worked up for sesquiterpene alcohols.

AU three distillates are now redistilled separatefy, the crude
first-running ’’ at 10 mm., the other two fractions at 3 mm.

The first fraction is distilled up to 99° at 10 mm., and the
residue, consisting mainly of citronellal, is added to the “ crude
citronellal.”

The second fraction is distilled up to 105° at 3 mm., and the
residue is added to the “ crude geraniol.”

In this wa 3 ^ are obtained a “ final first-runnings ” (about 5 per
cent, of the citronella oil used), and 50 to 52 per cent, of “ teclmical
citronellal,” which contains about 75 per cent, of pure citronellal,
and is worked up for “ d-citroneUol.”

By the redistillation of the third fraction (“ crude geraniol ”)
there is first obtained a little citronellal, which is added
directfy to the “ technical citronellal.” The main fraction,
namely, “technical geraniol,” comes over at 115° to 120° at
3 mm. The residue is added to the contents of the enamelled
container.

In order to convert “ technical geraniol ” into “ pure geraniol ”
it is necessarj’^ to remove completely the small traces of citronellal
which spoil its odour. This is done by boiling for several hours
with dilute caustic soda, whereby the aldehyde citronellal is
resinified and remains in the residues on subsequent rectification.

253

PEItFU ME B.Y

The operation is best performed in a double-M^allecl iron vessel
fitted with a good reflux condenser. After boiling for four hours,
the mixture is diluted with cold water and the npjier oily layer
is separated from the lower aqueous layer. The oil is washed
twice V'ith lukev^arni water, then with 50 per cent, acetic acid
until just acid, next with sodium bicarbonate solution until again
allcalinc, and flnall}'- once more with Avater.

The oil is now distilled in vacuo from a 5-litre glass flask in an
oil bath (or, for larger quantities, from a copper vessel). Time
geraniol comes over at 115° to 11S° at 3 mm. as a Avater-clear
liquid. The yield is 95 per cent, of the “ technical geraniol.”

GERANIUM, OILS OF. — The true geranium oil must not
be confused AAith the so-called Indian (or Turlcish) geranium oil.
The latter is actually the East Indian palmarosa oil, an oil dis-
tilled from a member of the natural order Graminece (see under
” Gingergrass Oil ”), whilst true geranium oil is the pi'oduct of
various species of pelargonium belonging to the natural order
Gcraoiiacece. The principal species distilled arc Pelargonium
odoraiissimum, P. cajnlatum, P. gravcolcns, and varieties of
P. Padula, together with, in all probability, numerous hybrid
forms. According to E. M. Holmes (P. E. 0. P., 1913, 239),
the majority of the species of pelargonium are nathms of the dry
rocky slopes of South Africa, but in then’ natural surroundings
they are someAvhat stunted in groAvth. ^Yhen plantations are
laid out in the south of Europe or in Algeria, etc., the}’- are
general!}^ established on low-ljdng ground kept moist by a system
of irrigation, so that the plants groAA’ luxurious!}’- after attaining
a height of 2 feet 6 inches to 4 feet, AAith stems nearly an inch in
diameter. The result is that three crops of leaves can usually be
distilled annually AA’lien the groAvth is luxurious — as it is, for
example, in Algeria. This, hoAA’CA’-er, is not the ease in the south
of France. A considerable proportion of the geranium oil of
commerce is distilled in the island of Reunio2i, and is knoAvn as
Bourbon geranium oil ; a large amount is also distilled in Algeria,
and a certain amount is produced in Spain, Italy and Corsica.
According to Holmes {loc. cit.) the plant used at Grasse, so far as
can be judged from the leaf of the plant, appears to be Pelargonium
capitaium. The plant cultivated in Bourbon is generally stated
to be the same species, but -the Bourbon-distilled oil more nearly
corresponds in odour Avith that of the allied species Pelargonium
graveohns.

In Grasse the plants are propagated by means of cuttmgs, set

254

PEBFU MERY

out in October in sheltered beds, protected in frosty -weather by
means of straw mats. The cuttings are taken from the nurseries
in April and planted out in open fields, where, under verj- favoim-
able conditions, they will grow to 4 feet m height. In the
neighbom’hood of Kice they flower in August, but in cooler
districts, such as Grasse, in October. The time of cutting in
Algeria lasts from early spring until mid-autumn. In Bourbon
the cutting proceeds during nearty the whole year. It has been
found that the best jdeld of essential oil is obtained after a few
da 3 's’ rain, and when the leaves are gathered in tlic earlj' morning
before the buds have opened. The first crop in Bourbon is taken
in April, the second in June, and the third in October. The
plants require careful handling, as when the leaves are crushed
there is always a loss of essential oil. In Reunion, as well as in
Algeria, every geranium farm of anj'- importance possesses its ovti
still. In most cases care is taken to emplo^y a form of still with
a double bottom so that the leaves are not burned.

According to Cordemoj'- {Rev. cultures coloniules, 1904, 14, 170),
the species cultivated in Reunion is Pelargonhim capiiatum (but
see above). The plant flourishes best here at altitudes between
400 and 1,200 metres, the lugher regions bemg too cold in the
winter time. There are between 250 and 300 distillers of tlic oil
in the island. About 700 to 1,000 kg. of geranium leaves are
necessar}’- to 3 'ield 1 kg. of oil.

In Corsica an excellent oil is produced on a small scale. Pelar-
gonium odoratissimurn bemg the principal species used. A few
modern steam stills have been installed, and if modern methods
are applied and transport difficulties are overcome (and these
are very serious in Corsica), there is undoubtedly a big future
for geranium distillation. As much as 1,300 kg. has been
distnied in Corsica in a year, but this is considerably above the
average.

Spain produces from 500 to 1,000 kg. of geranium oil in Valencia
and Andalusia.

■ According to Ducellier (“ Le geranium rosat. sa culture en
Algeria,” 1913, Algeria) there are about 2,200 acres m Algeria
planted -with geranium. There are plantations at Rovigo, Chelbi,
BoufarHi:, Borurian, MouzaiaviUe, Morocos, S. Faoueli, and other
places. According to this authority, only Pelargonhnn graveolens
is cultivated for distillation, and he considers, on the authority of
Knutt, that Pelargonium capitatum is a h 3 ’'brid of that plant.
Whilst the Algerian geranium is propagated b 3 ’- cuttings, it is not

256

PERFUMERY

necessary to renew the plantations every year as is done in the
south of France, as the Algerian winter is not severe enough to
kill the plants. In some districts they will live for ten to twelve
years. In Algeria, as in Spain and Reunion, three crops of leaves
are gathered annually — one in early spring, a second in June, and
a third in October.

The cultivation of the geranium j)lant is of paramount import-
ance if a good yield of oil is to be obtained. This is especially true
in the districts less favoured by natural conditions. Boutilly has
clearly established the fact that superphosphate of lime is very
favourable to high production of oil, and advises using tliis mamtce
to the extent of about 800 lb. per acre. One of the most successful
fertilisers for geranium plants is a mixtm-e of sodium nitrate
(200 parts), ammonium sulphate (150 parts), superphosphate of
lime (300 parts), and potassium sulphate (150 parts). (See also
P. c& E. 0. R., 1913, 381, for cultural details.)

The leaves are the odom' bearing portion of the plant, the
flowers being practically odourless. Sometimes the oil is redistilled
over rose petals, or rose petals are added to the geranium leaves
when distilled. The resulting oil is, of course, of exquisite odour,
and is sold as “ oil of rose-geranium.”

Charabot and Laloue have studied the development of the
odorous constituents in the geranium. They found that these were
entirely absent in the petioles and stems, and were only to be found
in the leaves, where they appear to have their origin. The oil was
distilled from the green plants in July, and again, from exactly
similar plants, in August. These two distillates were found to
have the following characters : —

Specific gravity
Optical rotation
Acid number
Esters

Free alcohols .
Total alcohols .

July.

0-897
— 10 °

43-8

5-8

67-8

per cent.

August.

0-899
— 10° 16'
41

62-1

68-6

per cent,

It was thus shoAvn that (1) the acidity decreases as the
plant matures, (2) the oil becomes richer in esters as grovi}h
proceeds, (3) the amount of total alcohols increases slightly
and the amount of free alcohols decreases slightly as vegetation
proceeds.

They also obtained interesting results in the examination of the
oil separating from, and the oil dissolved in, the distillation waters

266

PEBF V -V E E Y

of immature plants. These oils, and the ttvo buUted, had tho
following characters : —

Separated oil.

Soluble oil.

Total oil.

Specific pravity

0-898

0-893

0-897

Optical rotation ,

- 11°

- 5° 13'

- 10° 6'

Acid number

16-5

Ester number . . j

1 16-6

6*7

1 15

Saponification number .

63-G

23*2

1 57

Total alcohols

70 7 per cent.

77'5 per cent.

7T8 per cent.

Esters

7*0 per cent.

2*8 per cent.

6*3 per cent. ^

According to Furukawa {Jour. Chem. Ind. Tohio, 1919, 22, 83),
experimental cultivation of three species of geranium has been
carried out on a farm near Tokio. These are Pelargonium gravcolens,
P. radula, and P. deniiculatum. The oils distilled from the first
two did not resemble geranium oil of commerce, whereas that
from P. dcnticulatum resembled commercial geranium oil to some
extent. The three oils had the following characters : —

P. gravcolens.

P. radula.

P. dcnliculalum.

Specific cavity .

0-9178

0-9234

0-886

Acid number

183-6

5-6

7-17

Ester number

4-8

31-7

12-8

Free alcohols

22-1 per cent.

17-26 per cent.

■ 60 per cent.

Total alcohols

26-3

63-5 per cent.

Yield of oil

1-7^2 „

1-0

Optical rotation .

+ 4° 6'

+ 3°

Puran Singh {Indian Forest Records, v., part viii., 1917, and
P. & E. 0. R., 1917, 8, 327) has reported upon the wild geranium
of the Nilgliiris. He states that tliis plant is Pelargonium gravcolens
{P. terehiniaceum, Harv. and Sond.). A yield of 0-044 per cent,
of the weight of the entire plant was obtained, the essential oil
having the follovdng characters : —

Specific gravity at 16° .

Optical rotation
Eefractive index at 18°

Total geraniol
Free geraniol
Esters as geranyl tiglate
p- 257

0-888
— 5° 39'
1-4600

74-8 per cent.
46-6 „

40-12

PEBFU M FjBT

The following values may be taken as covering practically all
pure geranium oils from the sources named : —

Bourbon.

African.

Specific gravity

Optical rotation

Refractive index

Esters as geranyl tiglate .
Total alcohols as geraniol .

0-888-0-897
- 7° 50' to - 14°
1-4G20-1-4685
22-33 per cent.
67-77 „

0-892-0-904
— 6° 50' to — 12°
1-4640-1-4720
18-30 per cent.
65-78 „

French,

Spanish.

Specific gravity

Optical rotation

Refractive index

Esters as geranyl tiglate .
Total alcohols as geraniol

' 0-895-0-905

— 7° to — 11°
1-4630-1-4065
20-30 per cent.
70-76

0- 896-0-907

— 7° 20' to — 12°

1- 4640-1-4675
26-42 per cent.
65-79

Corsican.

Sicilian (?)

Specific gravity

Optical rotation

Refractive index

Esters as geranyl tiglate .
Total alcohols as geraniol .

0-895-0-904
- 8° to - 11°
1.4640-1-4680
23-28 per cent.
68-76

0-894-0-901
- 9° to - 11° 30'
1-4645-1-4600
26-35 per cent.
65-77

The figures given above for Sicilian oil must be accepted with
reserve. According to Pellini [Ann. di Clmn. A'pjMc., vii., 3),
Pelargonium capitatum is the only species found in Sicily, and the
following figures were obtained for four samples of oil distilled
from the earliest to the latest period of flowering : —

Specific gravity

0-915

0-899

0-909

0-902

Optical rotation

- 5.40°

— 6.56°

— 6.14°

—

Refractive index at 25° .

1-4686

1-4647

1-4670

1-4653

Per cent.

Esters ....

38-77

30-04

40-12

38-39

Total alcohols .

47-1

60-3

69-7

258

p KBF r 2r E B y

A]] geranium oils should be soluble in Tolumes of 70 per cent,
alcohol. The principal constituent of geranium oil is the alcohol
geraniol C^oHigO, in the free condition to the greater extent, and
to a lesser extent in the form of esters, of •which the tiglic acid
ester is the principal. There is also present a notable amount of
citronellol CjqH„pO, ■svhich, together with the geraniol and very
small quantities of several other alcohols, makes u'p the “ total
alcohols as geraniol." The proportion of citronellol to geraniol
varies in the different types of geranium oil. In Spanish oils the
citioncllol forms about 35 per cent, of the total alcohols, whilst
in African oils only about 20 per cent, of the total is citronellol.
In Bourbon oils the two alcohols are present in about equal
proportions. Linalol, tei-pineol, menthol, phenyl-ethyl alcohol,
and possibly borneol and amjd alcohol, are also present. Pinene,
phellandrene, menthone, and citral are present, and traces of
dimethyl sulphide (in Bourbon oils).

Geranium oil is largely used in perfumery, very large quantities
being consumed in the manufacture of high-grade soap. The oil
was at one time largel}’ adulterated in a very crude fashion.
To-day, owing to the ease with which the cruder adidterants are
detected, adulteration is less common, and where it is practised
it is on a more scientific basis. Palmarosa oil and artificial esters
are sometimes used.

E. M. Holmes (P. E. 0. R., 1913, 372) gives the following
interesting list of hybrid pelargoniums (the majorit}’’ of which
have had their relationships indicated by klr. J. Eraser, of Kew)
as showing the extent to which the alteration in odour may go
by hybridisation. The relationships of those marked with an
asteri.sk are on the authority of Eraser ; the remainder are
classified by E. M. Holmes.

Weak citronellal.
Ladanum.

Pelargonkim adulterine m
*Lady Mary .

*Duchess of Devonshire .
P. angiihsum (-f cecvllatvm)
*Pretty Polly

P. hlattarinm
P. capiiatum

*var. conspicunm .

*Dale Park Beauty
^Kimberley .

*Mrs. Kingsbury .

Eaint rose, ladanum, and

citroneUal.

CitroneUal, slight ladanum.

Eaint rose, ladanum, ‘ and

citronellal.

Rose, ladanum, faint butyric.
Ladanum and pepper.

Eaint rose and ladanum.

260

17—5

PWBFU M E nr .

^Lucerne
'^Old Unique
Scillonian .
*Sliottenden_Pet .
P. crispum.

var. compactum
Clyne’s Seedling .
P. clenticulatum.

*var. fiUcifolium
Pheasant’s Foot .
P. fragrans
P. gratum
P. graveolens
^Little Gem
*Monsieur Nonin .
^Scarlet Pet
*Westonbirt .

P. papilionaceum
P. pinnatum

P. qiiercifolnim.

Guriy .

Agnes

Danesford .

*Fair Ellen .

*Fau.’ Emily .

*Miss Dorrien Smith
Sweet Ellen
P, quinquevulnera
P. selechim
P. iomenfosum.

^Godfrey’s Bride .
P. vitifoliwn.

*Mrs. Babington .

Fault rose and tansy.

Slight rose and strong ladanum.
Bose and citronellal.

Bose and faint peppermint.

Citronellal, famt rose.

Bose and citral.

Faint butyric and ladanum.

Bose, ladanum and faint butyric.
Fault rose and tansy.

Tansy and faint nutmeg.
Citronellal.

Faint rose, peppermint, ladanum.
Ladanum, slightly butyric.
Ladanum.

Bose, citronellal, and ladanum.
Citronellal, slightly mousy odour.
Bose, ladanum, and slightly
butvric.

Ladanum, faint citronellal.

Strong pepper.

Ladanum and faint peppermint.
Ladanum.

Faint citronellal, ladanum.
Ladanum, faint rose.

Shght citronellal, ladanum, pepper.
Citronellal.

Bose and citronellal.

Peppermint and faint rose.

Weak rose.

GERANYL ACETATE. — ^This ester, of the formula CjqHi^.
OOC.CH3, is of very great importance to perfumers. It is a
constituent of many essential oils, and is used on a considerable
scale in the manufactme of numerous artificial perfumes, especiall}^
those which are required to have a rose effect. It is prepared
artificially by heating geraniol and acetic anhydride in the presence
of sodium acetate, washing the resulting oil with water, and
finally rectifying under greatly reduced pressure. When pure,
geranyl acetate has the foUoAving characters : —

Specific gravity at 0° . . 0*9388

Specific gravity at 15° . . 0*9174

Boding point. , . . 242°-245°

Befractive index . . . 1*4628 at 15°

260

PEBFV MERY

It is not easy on a commercial scale to manufacture this ester
in a state of absolute purity, but good-qualit}^ samples as met
uith on tlie market should have an ester content of not less
than 95 i^er cent., and should give figures approximating to the
above. Geranyl acetate forms the prmcipal constituent of the
essential oil of Evcahjpias 2Iacar{hiri (q.v.), in which it occurs,
to the extent of over G6 per cent., associated with about 10 per
cent, of free geraniol.

GERANYL BENZOATE.— This ester, C10H1_.COO.CcH5, is
used to some extent in the compounding of artificial floral bouquets.
It is prepared by mixing 3 kg. of geraniol vdth 1-5 lig. of pyridine,
cooling to ice temperature, and adding, with constant agitation,
2-5 kg. of benzojd chloride, avoiding any substantial rise in
tempcratm’e. The mixtm’e is allowed to stand for several hours
at ordinary temperature, and the separated oil is washed, first
with water and then with a dilute warm solution of sodium
carbonate. The resulting oil contains unaltered geraniol, but it
cannot be purified by rectification, as it is partially decomposed
on distillation, even in vacuo. If, however, the product be washed
until a 50 per cent, solution of sodium salicylate, the unaltered
geraniol is dissolved out and the product becomes considerabty
richer in true geran}! benzoate. The pure ester boils at 195° at
a pressure of 15 mm.

GERANYL BUTYRATE.— Geranyl butyrate CioH^.OOC
(CHcla-CHg is an oil of sweet rose odour, finer than that of geranjd
acetate, and of great value to the perfumer. It is prepared by
heating geraniol dissolved in pyridine with butjnyl chloride, and
is an oil boiling at 143° at 13 mm. pressure. It is used to advantaee
in the preparation of artificial otto of rose and in many artificial
floral perfumes. Its specific gravity is about 0'892, and refractive
index 1'4550.

GERANYL FORMATE. — ^This ester, CigHi^OOC.H, is one
of the most valuable of the geranyl esters to the perfumer. It has
not been found in any essential oil, but may be prepared artificially
by allowing formic acid to react in the cold with geraniol in the
presence of .a trace of sulphuric acid as a condensing agent. It
has a fine rose odour, somewhat like that of the tea rose, or,
perhaps, “ green rose leaves.” It is, when pure, an ofl. boiling at
114° at 15 mm. pressure ; but it is impossible to manufacture it
in a pure condition on the commercial scale, so that the com-
mercial ester rarely contains more than 95 per cent, of actual ester.

201

PERFUMER Y

A good-quality geranyl formate should have a sweet powerful
odour, free from any trace of “ acid ” odour, and should have the
following characters : —

Boiling point at 3 mm.
Specific gravity
Optical rotation
Befractive mdex .
Actual ester

88 °

0- 920-0-927
0 °

1- 4640-1-4665

at least 95 per cent.

GERANYL ISOBUTYRATE. —This ester, CieHi-.OOC.
(CHllCH^la, is isomeric with and similar in odour to geranyl
butyrate. It is an oil which boils at 137° at 13 mm. pressure.

GERANYL ISOVALERIANATE.— This ester has the for-
mula CiiHi 700 C(C 4 H 9 ). It has a modified rose odour and is
capable of imparting a very characteristic note to artificial rose
perfumes. Its specific gravit}'- is about 0-890, and refractive
index 1-4570.

GERANYL PROPIONATE. — ^This ester, which is inter-
mediate in character between the acetate and the butjT-ate, has
a specific gravity about 0-9025, and a refractive index 1-4580.

GERANYL TIGLATE.— This ester, CioHi^.OOC.ClCHg) :
CH.CHg, is the characteristic odour bearer in geranmm oil. In
the determination of the esters in this oil they are always returned
as geranjd tiglate, which requires a different calculation from that
for linatyl acetate. Geranyl tiglate is a liighly odorous oil "with a
sweet rose-geranium odour.

GINGER. — ^This highty aromatic substance finds its principal
employment as a spice. The resinous matter and the high boiling
constituents of its essential oil, however, have a high fixative
value, and to a small extent it can be used to advantage in per-
fumery. Ginger of commerce is the dried rhizome of Zingiber-
officinale, probably a native of tropical Asia, which is largely
cultivated in the East and West Indies, in China, in Africa (Sierra
Leone), and to a small extent in Australasia. The method of
cultivation in Jamaica, which produces the most esteemed ginger,
is as follows {Bull. Botanical Dept, of Jamaica, December, 1891) :
“ The most suitable soil for ginger culture is a weU-drained clayey
loam. The land should be well dug and cleared of weeds. Small
pieces or protuberances of the root, 1 or 2 inches long, are planted
during Slarch or April, 4 inches deep and 9 to 12 inches apart.
It is well to cover the land with a moulding of dead leaves, straw
or litter, mixed witli manure. In a few months the whole ground

262

P ERF U M ERY

will bo covered. The flowers appear in September. When the
stallis wither, in the following January or February, it is time
to dig up the roots. When the tubers have arrived at maturity
and have put forth stems, they are fibrous, but before this takes
place they are still succulent, and, if recpiired for preserving, should
then be taken up. Ginger is an exhausting crop on the soil, and
should not be planted on the same ground two consecutive years.
The j-ield per acre is said to be 4,000 lb. and upwards.”

Guiger rhizomes are sometimes imported in the soft juicy
condition known as green ginger, but the ordinary gingers of
commerce are washed, dried, and scraped (uncoated ginger), or
are merel}' washed and dried (coated guiger). It is also sometimes
bleached or coated uith lime to erroneously suggest bleaching.

Sawer {OclorograpMa, ii., 95) gives the foUoiving account of the
cultivation of ginger in India as carried on in the hill states
adjoining the Ambalah district : —

“ Ginger is principally produced m Mahur Massa, Patra, Darva,
Kotlii, Kotahi, Bagal, and Jayal. The best pieces of last year’s
harvest are selected and placed in the corner of a house in the
month of Phagan ; the heap is then smeared over and covered
with cow dung to keep the roots from drying up in Har month,
w'hen the first rain falls. The land is ploughed up two or three
times and then divided off into beds,' with a little raised edge
round each bed, care being taken to make openings to let super-
fluous water run off ; for if w^ater stands on the crop the roots
will rot. Little pieces of the roots are then buried 3 inches deep
in the soil at intervals of 9 inches, and the field is next covered
over with the leaves of trees, w^hich keep the soil moist, and over
the leaves is spread manure to a depth of | inch. When it rains,
the water, impregnated with manure, filters rapidly through the
leaves to the roots. Artificial irrigation is not employed while
the rainy season lasts, but from Assuh to Poh it is necessary. In
the month of Poh the plants are about 2 feet high. In the months
of Sawan, Bhadon, and Assuh the field is weeded three times.”

According to Ridley (” Spices,” Macmillan & Co., London,
1912), there do not seem to be many forms or varieties of the
plant, as mi g ht be expected from the propagation being almost
entirely by means of cuttings. •

The Malays are acq^uainted with three forms, which they know
under the foUo^ving names : —

Halyia hetul (true ginger) is the name given to a form with
broad leaves and a very white-fleshed rhizome. It is taller than

263

PERFUMERY

the other varieties, and is used for making sweetmeats and as an
ingredient in curries.

Halyia hara or Halyia padi {bara = hot coals ; padi = rice) is
a smaller plant than the former, and is of greater pungency. It
is used locally in medicine.

Halyia Jmdang is of a redder tint than the others, and is used
in native medicines.

In Jamaica the planter divides the plant into “ blue ” ginger -
and “ yellow ” ginger, so called from the tint of the rhizome.
Blue ginger is also known as “ flint ” ginger, and the j’^ellow
variety as “ turmeric ” ginger. According to Kilmer, the plants
producing these varieties cannot be distinguished except by the
tints of the rhizomes. He suggests that blue ginger is a degenerate
form. The root of the blue ginger is hard and fibrous, and is of
less value commercially than that of yellow ginger.

Canton ginger, which is known in this country in the form of
preserved ginger, appears to be a more distinct variety. The
rhizome is thick and succident, hence its use as a sweetmeat. It
is said that it cannot be di’ied in Canton on accoimt of the absence
of sufficient sun heat in the season when the rhizome is dug.
There has been a good deal of confusion as to the plant from
which the Chinese ginger is obtained. In 1891 plants stated to
be the source of Canton ginger were sent to Kew Gardens, and
were identified as Alpinia galanga, but it is now established that
these were the VTong plants, and that Chinese ginger is actually
the product of Zingiber officinale.

Ginger was, according to E-idley {loc. cit.), one of the earhest
Oriental spices known to Europeans, and was certainly known
to the Greeks and Romans. The name zingiber (ginger) is
probably derived from the Sanskrit sangabib through the Arabic
zanzabib. The Greeks and Romans appear to have obtained it
from the Arab traders in the East, who doubtless brought it
from India. Its original home is not known, as no one seems to
have met Avith it in a wild state. The spice was well known in
England before the Norman Conquest, and in the thirteenth and
fourteenth centuries was nearly as common in trade as pepper.
■'One pound was, at this time, worth about as much as a sheep.

In the fourteenth century the Italians classified ginger in three
forms : —

{a) Baladi, coimtry or wild ginger.

(6) Golumbmo, that imported from Columbum (Quilon, in
southern India).

2G4

PER-F U MER T

Zd.'irco Polo is probably the first traveller who records having
seen the plant alive (12S0-1290). He met with it in Cliina,
Jialabar, and Sumatra. It was described in 1292 bj’’ John of
Montecorvino, and later by Xicolas Conti.

Preserved ginger in .syrup, or green gmger, was imported into
Europe as a sweetmeat as early as the Jliddle Ages. As the
rhizomes of ginger are very easilj' transported in a living state
for considerable distances, it is not surprising that the plant was
introduced into America very soon after the discovery of the
Xew World, and before am’- other Oriental spice. It was brought
to Xew Sixain (l\Icxico) by Francisco de Mendona, and the rhizomes
were e.’cported from San Domingo as earh* as 1583, and from
Barbados in 1G94.

Ginger itself is not adulterated to any great extent, although
from time to time ground ginger mixed with the powdered
exhausted spice is found on the market, and sometimes samifies
are found until too much mineral matter.

Preparations in the liquid form, however, which, from their
name, would appear to be made from ginger — such as essence
of ginger, ginger ale, ginger beer, and similar preparations — are
very frequently adulterated with capsicum, so that a fictitious
strength is given to the preparation at a trifling cost.

A. H. Allen {Analyst, xls., 124) gives the following anal3’ses for
pure gingers : —

per

Per

cent.

rent.

1. Total ash • • . .

3-54

C-23

4-41

5-15

6-53

7-GO

5-39

2, Ash soluble in water

2*3G

2-59

2*22

2-57

2-87

2-3G

—

3. Alkalinity of 2 as K«0

0‘9G

0-96

0*29

0-13

0-15

0*20

—

4. Extracted by 90 peV cent, alcohol

7*33

7-70

7-37

C-22

8-45

—

4-65

i>. Extracted by proof spirit

20-95

19-7

10-7

10-45

7-55

21-6

5*85

6, Extracted by cold water .

14-G

13-16

14-95

14-55

14-5

14-G

8-14

I i

K '

—

Per

cent.

1. Total Ash . , . .

3*61

3-19

2-72

3-52

3-29

' 4-5

1 — .

2, Ash soluble in water

1-24

1-45

0*69

, Ml

0-97

i 1-37

, —

3, AlJ:alinity of 2 as K^O

0-20

0-23

—

1 —

4, Extracted by 90 per cent, alcohol

—

I G-88

i 7-86

1 —

1 . —

1 —

5. Extracted by proof spirit

mSSm

' IG-l

! 11-8

12-4

—

6. Extracted by cold water .

8*33

I 9-8

1 8-5

7-2

8-1

7-4

205

PEB. F U M'E B T

The following analyses are due to Richardson : —

Snmplc,

Moisture.

Es’cntlnl

oil.

Fixed oil,
and
Ec^In.

Starch, j

Fibre.

Nitrogen.

1. Calcutta

Percent. ,

9-G

Percent.

7-02

Percent.

2-27

Percent.

4-58

Per cent.

49-3

Per cent.

7-45

Percent

1-01

2. Cochin.

9-41

3-39

1-84

4-07

53-3

2-05

1-12

3. Unbleached Jamaica

10-49

3-44

2-03

2-29

50-G

4-74

1-74

4. Bleached Jamaica .

11-0

4-54

1-89

3-04

49-3

1-70

1-48

5. Bleached Jamaica .

10-11

5-58

2-54

50-7

7-G5

1-4G

For the detection of capsicum in preparations of ginger, Garnett,
Grier, and La Wall {Analyst, xxxiv., 321) recommend the follo’idng
method. The liquid, such as ginger ale, is warmed to expel COo
and alcohol, if present. The aqueous residue is rendered acid
with dilute sulphuric acid and shalcen with 50 c.c. of ether for a
minute. If the residue from the ether, which is allowed to
evaporate spontaneous^, weighs less than 10 mg., it is treated
witli 2 c.c. of ^ alcoholic caustic potash solution. An additional
1 c.c. of the alkaline solution is added for each further 10 mg.
of residue. Tlie mixture is gently heated to boiling on a water
bath for thirtj'’ minutes under a reflux condenser. The alcohol
is then poured off, water added, and the liquid well shaken Avith
ether. The ether is separated and evaporated. If the residue has
a hot pungent taste, capsicum is present. One part of capsicum
in 10,000 parts of liquid can thus be detected.

The essential oil distilled from the true ginger rhizome has a
liighl 3 ’- aromatic odour, but is free from the pungent flavour of
the spice, which resides in its resinous constituents. The rhizome
^delds from 2 to 3 per cent, of a greenish- 3 ’'elloAA' oil having the
following characters : —

Specific gravity ■ . • 0-874-0-SS6

Optical rotation . . . — 25° to — 50°

Refractive index . . . ]‘4-S85-l*4950

Acid value .... 0-2

Ester value .... 1-15

Ester value after acetylation . 30-45

Oils AAull bo found, however, from time to time whose characters
fall outside the above limits. Bacon, for example {Philippine
Jour. Sci., 1910, 5, 259), examined a sample distilled in the
Philippines which had an optical rotation + 5*9°. Japanese oil
has been found having a specific gravity 0'894, and optical

26C

PERFUMER Y

rotation -f 9 ° 40 '. A Java oil has been found vith an optical
rotation -f 13 ° 9 '-

The oil consists principally of the terpenes J-camphene and
jS-phcllandrene, vith a sesquiterpene (or mixture of sesquiterpenes)
laiou'n as zingiberene. Cineol, citral, borneol, methyl-heptenone,
nomd aldeh3'de, linalol, a sesquiterpene alcohol named zingiberol,
CisHogO, and various esters have been detected in the oil. The
princiiDal odour hearer is probablj^ zingiberol.

GINGERGRASS OIL. — This useful perfume oil is con-
veniently considered in conjunction uith palmarosa oil, the so-
called East Indian geranium oil. (See “ Geranium Oils.'’) Con-
siderable m3’-stery has for man3" 3’ears surrounded these two oils,
and the questions involved cannot 3*et be regarded as solved.
So late as 1893 the authors of “ Pharmacographia Indica ” stated
of the oil distilled from Andropogon SchccnantJms (which, however,
is to-day renamed Cymhopogon Martini), that : “The oil distillers
in Khandesh call the grass Moiiya when the inflorescense is young
and of a bluish-white colom- ; after it has ripened and become red,
it is called Sonfiya. The oil obtained from it m the first condition
has a more delicate odour than that obtained from the ripened
grass. The mot^a oil is usualty mixed mth the second kind,
which, b3’- itself, would not fetch a good price in the Emopean
market. (This ma3'- to a great extent account for the considerable
difference in the qualit3' of the two commercial grass oils, the so-
called geranium oil and ginger grass oil).”

For man3’^ 3-ears gingergrass was regarded on the London market
as merel3’’ adulterated palmarosa oil. It appears certain, however,
that the two oils are tAvo quite different j)ure oils, and that the
statement quoted above from the “ Pharmacograpliia Indica” is
incorrect. The grass Cymhopogon Martini exists in two forms,
whose botanical differences have not been made out. The nath-e
name for the grass is Roslia or Rusa grass, and the two forms arc
knovTi as Motia and Sofia. The motia grass yields palmarosa or
Indian geranium oil, whilst the sofia grass 3delds gingergrass oil.

The grass grows, according to Dr. D 3 unock, freel3>-, tliough not
very widel3-, on open hill sides in West Khandesh, especial^ in
Akrani. According to a report b3'- R. S. Pearson {Indian Forest
Records, vol. v., part vii.) the most important localities from which
Rosha oil is obtained in the Bombay Presidenc3'^ are. North, East,
and West Khandesh, and the North and South Nasik Divisions
of the Central Circle, and to a less extent from the Surat Dangs
and Ranch Mahals Divisions of the Northern Circle. In these

207

PERFUMEBY

localities the bulk of the grass comes from the Shahada, Taloda,
Pimpalner, and Akrani Ranges of Khandesh, while the Central
and Northern Ranges of the Noi’th Nasik Division also produce
considerable quantities.

Aecording to a reijort received from Messrs. Volkhart Brothers,
Ltd., Khandesh and Nasik were formerly the chief exporting

Naixio^of

Circle.

Name of
Division.

Approximate area for which
leases are given for the collec-
tion of Rosha grass.

Remarks.

Berar ' .

Mclgliat

Acrc.s.

Open forests A . 220,513
Dense forest BJ . 522,459

' Total . 742,972

Generally the “ Motia ”
grass is found in class
A and the “ Sofia "
in class B forests.

* > •

j Niinav .

j No information available,

1 though the area is

1 knowntobelarco.

J > •

BctuI

''80,930

Buldana

33,430

I In the Ycotmal Pusad
Taluqa.

Alcola .

4,788

In the Narnala block.

1 f

Aniraoti

31,199

In the Morsi-Warud and
Amraoti Ranges.

Northern

Clilund-I

Reserved forest |

In the Ambara Range.

wara J

\ 20,000

In Ryotwari and IMal-
guzari lands.

Saugor .

Small quantities only
available.

> }

Southern

Mandla .

• • . .

Area not knovm.

Bakhgat

Only a very small
quantity of “ Sofia ”
grass available. In
other parts of this
- Circle the grass is
not available in com-
mercial quantities.

districts in India, but now they are of less importance than tlie
Berars.

The most important areas from which Rosha grass is obtained
in the Central Provinces are in the ]\Ielghat, Betul, and Nimar
Forest Di\dsions of the Berar Circle. The grass is found else-
where, scattered in small quantities through the forest, and
though distilled in some divisions it is not Avorked on an
extensive scale.

208

PEBF V 2IEP T

The table on p. 2GS give-s the approximate areas in eacli
division in which leases are annually given for the collection of
Eosha grass.

The most important areas from which Eosha grass is obtained
in Central India are the Ali Eajpur. Jhabua, Dhar, and Barwani
States, of which the Jhabua State is the most important. In Ali
Eajpur, Eosha grass is found growing in the southern and western
parts of the State and nearlj' all over the Jhabua State, while in
Dhar it is found in limited quantities in the Mandu, Dharanpuri,
Kukshi, and Nananpur Eanges. In Barwani State, Eosha grass
is found in large quantities in the Narbadda and Pati Eanges,
and in limited quantities in the Silawad, Pansemal and Eajpur
Eanges.

The areas over which Eosha grass is found growing in Ali
Eajpur, Jliabua, and Dhar States is not known, while that in the
Barwani State is given by the local authorities to be as follows : —

JTnmo of
State.

1 i

Name of Range. |

Approximate
area for
which leases
are given
for tho
collection of
Rosha grass,
in acres.

Average
No. of
tons of
grass ex-
tracted.

Remarks.

Banvani

/Narbadda Range '
Pati Range . !

^ Silawad Range . ‘
Pansemal . ;

i^Rajpiir Range . j

48,870

87,080

34,905

34,301

3,745

} {
13

33i-

These two Ranges
are leased together.

In 1909-10 no grass
was available.

In 1911-12 and 1912-
13 no grass was
available.

A certain amount is also available for distillation in Madras.

Pearson (loc. cit.) states that the local practice, which is the
only method used at present for extracting the oil, is bj" direct
fire-heated stills, steam stills having been used onlj’ experimentall 3 ^
The flower and leaf, and small portions of the stem are used for
distillation. The flower and the upper third of the stem are
collected in September and October, being tied into bundles or
“ pulas ’’ of about 4 oz. each. A second cutting is frequently
made when the grass flowers for its second time. The grass is
either distilled in a partiall 3 ' green state, or the flower heads and
portions of stem are carefullj* dried in the shade before distilla-

200

p E li F V ii/ E n y

tion, during Avliicli process they lose from 20 to 40 per cent, of
their weight. The plant used by the local distillers varies but
little from district to district, being always of a primitive tj^pe.
The still is always erected quite close to a stream or pond, so as
to provide plent}’’ of water for condensation puiqioses. The still
itself is of iron or copper, and is cj'lindrical in .shape, having a
large opening at the top for the introduction of the charge. The
stills hold from 12 to 14 gallons, and are charged with 1 part of
grass and 4 parts of water, and then heated over a naked fire.
E.xperiments carried out by j\Iessrs. Pheroze & Co., of Bombay,
resulted in a yield of 0-87 per cent, of oil by distilling the entire
plant, which consisted of 54 per cent, of stalks, 28*5 per cent, of
leaves, and 17-5 per cent, of flower tops. When these portions of
the plant were distilled separately, the following yields of oil were
obtained ; stalks, 0-04 per cent. ; leaves, 1*32 per cent. ; flower
tops, Iwl per cent. The yield, however, is variable, and may
reach 1 per cent, on the fresh plant, and nearly 2 jjcr cent, on the
dried plant.

The industry is a very important one, the annual distillation
reaching from 80,000 to 120,000 lb., possibly even more.

Messrs. Volkart Brothers state that Piosha oil, both “ Motia "
and “ Sofia," is consumed all over India for tlie mahufacture of
native “attars." Calcutta, Benares, and other places in northern
India take as much as 3,000 to 5,000 lb. annuall}^ for this purpose,
the oil first finding its way to Bombay, from which place it is
sent to the north. In addition to the above quantit}^ 3,000
to 4,000 lb. of this oil finds its wa}'’ direct to Burhanpur in the
Nimar district, where it is made up local!}" into “ attars.” Prob-
ably .small quantities are also retained in the producing districts
and manipulated locally, but on this point no reliable information
is available.

A. D. Bhote, a Range Forest officer in the Central Pro^dnees,
states that Rosha oil, and especially “ Motia,” is considered to be
a good remedy for rheumatism and is sold for this piu’pose in
most Indian bazaars. It is also used to a limited extent for
scenting soap. The oil is considered to be a cooling astringent
and is used in the case of headaches, for skin diseases, and is said
to be a cure for baldness ; it is never taken internally, however,
except in veiy small doses as a cure for bilious complaints.

Its cliief use in India is for adulterating “ attar " of roses,
either by dilution of the “ attar ” or by sprinkling the rose leaves
with Rosha oil before distillation takes place. Bhote states that

270

P E Ey U'M E E r

before using Rosha oil to adulterate rose ‘‘ attar ” it lias to be
refined ; this is done by shaking the Rosha oil with water mixed
wiili lime juice and then exposing it to the rays of the sim. This
is no doubt done to bleach the colour of the oil in order to make
it resemble “ attar of roses in colour. Further, he states that
Rosha oil which in the process of manufacture has been over-
heated is too dark in colour for use in adulterating rose “ attars."

Rosha oil, as found on the market in India, is rarelj’- absolutely
pure ; in fact it is nearly always heavily adulterated with tur-
pentine, linseed, rape, ground-nut oils, etc., the adulteration
being often carried out by the distillers themselves. On re-
distillation to obtain pine oil, a more concentrated and more
strongly perfumed oil is obtained, which is, however, not often
found on the Indian market.

R. S. Pearson (Zoc. cit.) has made the following suggestions for
improving the industry, and, considering that these two important
oils are practically a monopoly of India, it is to be hoped that
his suggestions will be acted upon : —

It requires no very deep knowledge of the JRosha grass industry
to arrive at the conclusion that the business is not being carried
on to the best advantage of everybody concerned. Ever; 5 d;hing
points to the desii’ability of introducing steam-distillation plants,
not only in order to obtain a greater quantity of oil from a given
quantity of grass, but to reduee the cost of production bj’- a saving
in fuel and labour.

Af ter carrj-ing out experiments with the steam-distiUation plant
in the Melghat Division, the foUoving conclusions have been
arrived at ; —

(1) That approximately 20 per cent, more oil can be obtained
from a steam plant than from a dii’ect-fire stiU when using
thoroughly sun-dried grass. Again, when using steam distillation
with dr 3 ’' and green grass, 100 per cent, more oil was obtained
from the latter for the reason that the oil has not time to volatilise
out of the green grass. The above are the two extremes, so that
were a plant erected of sufficient size to work off the grass nearly
as quickly as it came in, namely, in a partially green state, the
5 deld, when using a steam plant, would be at least 50 per cent,
greater than from the direct-fire stUl at present in use.

(2) That the consumption of fuel when using a boiler is some-
where about 100 per cent, less than that required for a direct-fire
still, and SO per cent, less than that required when using a modified
direct-fire still.

271

P JSBFTJ M E nr

(3) That the amount of labour reciuh’cd to work a steam still
is, if anything, less than that requu'ed for a direct-fire plant,
though the actual pay of a boiler nian, working also as an overseer,
is somewhat greater than that of an overseer necessary to supervise
the plant at present in use.

(4) That the rate of distillation in all three t 3 ^pes of stills is
about the same, though the time taken to charge and unload
a steam or modified direct-fire still is less than that requned for a
direct-fire still.

(6) That better results are obtained when working at 10 lb.
pressure in the boiler than at higher pressures.

(6) At present mo redistillation is carried out, the colour of the
oil being pale yellow, wliich on storage becomes darker, due to
oxidation. When distilling with either a direct-fire or steam still,
traces of moisture become emulsified with the oil, more so in the
latter case. To overcome this difficulty a simple anhydrous
sodium sulphate filter is recommended.

(7) It should be remembered that the rectified oH is water
white ; this can only be obtained by redistillation, which can
onty be done by adopting the steam process. Whether redistilla-
tion will pay depends entirely on the fluctuation of prices in the
market. It is a pomt that should be carefully borne in mind as
the industry expands.

(8) That where at present only one small still is worked in an 3 ^
one locality — in other words, where only small quantities of
Bosha gi’ass are available — ^it would not be worth while erecting
a steam plant, but that far better results than those given b 3 ’' a
direct-fire still would be obtained by using a modified direct-fire
still fitted with a false bottom, so that the water and grass should
not come in contact, thus introducing steam distillation on a
modified scale, as advocated by Dunbar Brander. Wliere, how-
ever, two spiall stills are at present worked a small portable steam
plant is advocated, which could be moved at least once in the
working season to another place after the grass in the first locality
had been exhausted. The third case to be considered deals vdth
such places as exist at the foot of the hills in the Melghat, where,
3 "ear after year, three or more Bosha stills are erected in one place
and where the grass is abundant. In such localities it would be
advisable to erect more permanent plants, consisting of an S-h.p.
boiler, four or more stills, and one condenser to ever 3 ^ two stills,
the whole covered in by a roof for the protection of the plant
during the monsoon months.

272

PERFUMER Y

(9) That the yield of oil when using a steam plant or a modified
direct-fire still varies little when using sun-dried grass, and that
the chief advantage in a steam plant is economy of fuel and
facility in regulating the duration and rate of distillation.

The characters of the Motia oil, or palmarosa oil, are very
admirably summarised by Puran Singh, Chemical Adviser to the
Forest Research Institute, Delna Dun {Indian Forest Records,
vol. V., part viii., p. 4G) as follows : —

The constants of the “ Motia ” oil have been determined by
various chemists from time to time, but it has always been
doubtful how far the samples examined could be regarded as
genuine. Besides, it is not known if the oil obtained by a modem
steam-distillation plant and subsequently refined has been put
on the market, and if its constants have been recorded. Through
the courtesy of Mr. C. E. 0. Cox, officiating Forest Economist,
Forest Research Institute, Delira Dun, the writer had the oppor-
tunity of examining crude oils obtained by steam distillation by
Mr. R. S. Pearson, and it may not be without interest to give the
constants of the oils as obtained in the laboratory of the Forest
Research Institute, Dehra Dun.

As regards the constants of the “ Motia ” oil recorded till now.
Parry (“ Chemistry of Essential Oils, etc.,” 2nd ed., p. 182) gives
a very acciuate summary : “ When pure the oH has a specific
gravity of from 0'885 to 0-896, and is almost inactive optically,
rotating from — 2° to -1- 2°, usually under 1° either way, and
rarely up to -f 4°. (Gildmeister and Hoffman, in their “ Volatile
Oils,” last edition, record a maximum of -f 6°.) The oil should
dissolve in tluee times its volume of 70 per cent, alcohol. Its
refractive index is about 1-4800. . . . The esters do not require
less than 3 nor more than o per cent, of potash for saponification.
The usual amount of esters present is from 10 to 15 per cent.
The free gcraniol varies from 65 to 85 per cent. The total geraniol,
free and combined, varies from 72 to 92 per cent.”

Some time ago Mr. Burkhill, the then officiating Reporter on
Economic Products to the Government of India, sent a number
of specimens of “ Motia ” oil collected by himself from the Indian
distillers to 3Icssrs. Scliimmel & Co., Leipzig. In their Semi-
Anmial Report for 1910 Messrs. Schimniel <b Co. published the
constants given in ihi tabb on p. 2'74 for these oih.

Even these samples were not of the very best quality that it is
possible to distil from the grass. The crude water-distillation
method as emploj’cd by Indian distillers is hlcely to affect the

r. 273 15

PEBFU MERY

quality of the oil injuriously. The water-distilled oil as put on
the market is, as far as it is known, never rectified, though Parry
mentions having met with rectified water-white Motia oil. In
this connection it may be remarked here that, according to the
Reports of Messrs. ScJmnmel & Co., this valuable Indian product
is losing its reputation in Europe owing to lack of uniformity in
the quality of the oil and to the prohibitive prices asked for it.
Both of these complaints can be easily removed, the first by
rectification of the oil, and the second by better methods of
distillation. At present, in small crude stills, the Indian distillers
cannot handle sufficiently large quantities of the fresh green grass
in the proper season, nor can they arrange to dry and store up
the grass for future use. By proper organisation and by improving
the distillation plant it is possible to increase the annual Indian

No.

Placo of
production.

cl.

lo°

a D

20°

Acid

No.

Ester

No.

Total

gera-

uiol.

Solubi-
lit}^ in
70 per
cent,
alcohol.

Cliitar .

■■

Pahnarosa

-f 0° 6'

oils (Molia

1-47225 1

oils).

0-8

39-8

Per cent.

91-5

1-5 vol.

Kumbi .

liSwiii

-f 0° 5'

1-47176

1-0

47-3

90-7

1-5 ,,

Moliana .

Ills 911 In

-f 0° 20'

1-47264

0-8

34-8

92-0

1-5 „

Naoli

IlK 111' il

-f 0° 15'

1-47205

0-5

40-7

93-0

1-5 „

Ragarwal

0-8946

-f 1° 20'

1-47382

0-8

38-4

88-2

1-5 ,,

Udhala .

0-8906

-{- 0° 35'

1-47225

0-8

38-7

92-4

1-5 „

output of the ofi. vdthout any extra cost, as it is well known even
to the Indian distillers that the green fresh grass has more oil in
it bulk for bulk than the late ripe grass of autumn. These im-
provements would go a great way to render the price of the oil
more uniform.

Rectification of the oils in a rectif^fing steam stiU, whether
originaUy obtained bj’- water distillation or steam distillation,
would give a standard uniform quahty of oil, which would make
the detection of adulterants very easy. If these improvements
are delayed, it is possible that the Indian trade in this article may
be lost.

For the purpose of this paper the following samples were taken
for examination. These are described below, and the constants
obtained for each are given in a tabular form on p. 276.

(1) The crude “ Motia ” oil obtained by steam distillation from

274

PER F U JI E R Y

green grass, distilled tliree to five days after cutting, prepared by
j\Ir. E. S. Pearson, Porest Economist. Distilled in October, 1914.
Taken for examination from the museum of the Institute in
August, 1915. The odour of the oil had gone bad, due to rancidity
caused by the presence of water and other impurities. Before
examination it was dried over anhj^drous sodium sulphate and
filtered. The constants were determined according to the methods
given in “Volatile Oils,” Gildmeister and Hoffman, 1st ed.,
pp. 185-195.

(2) No. 1 rectified by steam distillation, dried on anhydrous
sodium sulphate, and filtered ; 200 c.c. weighing 176 "grams
were redistilled, and 175 c.c. weighing 154 grams, or 87-5 per cent,
were recovered as a water-white, perfectly colomless oil. Odour
good, though very slightly affected by the original rancidity of
the oil taken.

(3) The crude oil obtained by steam distillation from the sun-
dried grass. In this case the grass was dried for about twenty-five
days. It was prepared by Sir. R. S. Pearson in October, 1914.
Taken for examination from the museum in August, 1915. The
odour of the oil was bad ovdng to the presence of water. It was
dried on anliydrous sodium sulphate and filtered.

(4) No. 3 rectified by redistillation with steam, dried on
anhydrous sodium sulphate, and filtered; 200 c.c. weighing

177 grams gave 165 c.c. or 145 grams, or 81'90 per cent, of
rectified oil. The colour was pale. Odour good, though very
slightly affected by the original rancidity of the oil taken.

(5) A genuine “ Motia ” grass oil received from Nimar and
Baldana Divisions, in the Central Provinces, distilled by water-
distilktion method by the Indian distillers in 1910 and stored in
the laborato^ 3 ^ Taken for examination in August, 1915, dried on
anliydrous sodium sulphate, and filtered. The odour was good.
Ikry slight rancidity. Colour yellow.

(6) No. 5 rectified by redistillation. From 200 c.c. weighing

178 grams, onl}^ 100 c.c. weighing 88 grams, or 49-5 per cent,
wore recovered for anal 3 -sis. Palish white ; odour good.

(7) No. 5 rectified by redistillation. From 200 c.c. weigliing
178 grams, 162 c.c., weighing 144 grams, or 81 per cent, were
recovered for anal 3 'sis. Colour, pale ; odoui* good.

Reading this table along vith the table of constants as given
b 3 ' J/cssr^. Sc7nm7nel cO Go., the improvement in the qualitv of
the steam-dislilled oil is evident as compared witli llic Avater-
distiiled oil. Tlic AA'ater-distilled oil has a specific gravity of from

276 IR— I

PE RFU M E P Y

0-8903 to 0-8946 at 15“ C., aud a five years old sample examined -
at Delira Dun had a specific gravity of 0-8925 at about 28° C.,
v-hile the figure for the crude steam-distilled oil is only 0-8818 and.

0- 8831 at 28° C. By drying the grass in sun the specific gravity
of the oil distilled from it is slightly increased. It is remarkable
that the old oil has given a rotation of + 5°, and the same rectified
to the extent of 81 per cent. + 6°, while the rectified fraction,
consisting of the first 50 per cent, of this oil, only -f 0° 16'. The
optical rotation in this case is high; usually the oil has an
optical rotation below 1° and, very rarely, up to -k 4° and even
4- 6°. In this case this rare maximum has been reached, the
slight increase over it being due to storage and oxidation due to
it. The crude steam-distilled oils rotate less than 1°, the rectified
being slightly more active than the crude oils. The refractive
index should be taken as fairly constant for aU oils, being about

1- 4700. The acid number of the crude steam-distilled oils is
about double that of the oils when rectified, but it is generally
less than those of the water-distilled samples.

The next important consideration is the geraniol content. The
total geraniol content of the crude and the rectified steam-distilled
oils is 91 per cent., the water-distilled old oil showing only 88 per
cent. But Messrs. BcUmmel <h Co. have recorded a total geraniol
content of 88 to 93 per cent. Parry has recorded 78 to 92 per cent.
This is, of course, due to the difference in the quality of the grass
distilled, which would depend on : (1) locality ; (2) the climate
(the total rainfall in the locality affects the quality of the oil) ;
(3) freshness of the grass when distilled ; (4) age of the grass
(the over-ripe grass yields inferior oil ; the “ virgin ” cuttings of
the grass give better oil than subsequent cuttings) ; (5) the

proportion of flowers to leaves and stem in the culms of grass
taken -for distillation, the finest perfume being in the flowers.
But 91 per cent, total geraniol content is usual in the steam-
distilled samples examined. This figure may vary slightly with
locality, but it must be admitted that the steam-distilled oils udll
tend to be richer in geraniol than the water-distilled oils. This is
further supported by the fact that in another place Messrs.
Schhnmel & Go. themselves have reported the figures given in the
table on p. 278 for four pure samples of Motia oil (Parry’s “ Chemis-
try of Essential Oils and Ai'tificial Perfumes,” 2nd ed., 1908, p. 187).

In these oils 92 per cent', geraniol is the maximum, and 77 per-
cent. the minimum, while free geraniol varies from 68 to 83 per
cent. The crude and rectified steam-distilled oils require about

•277

PEB F U M E B 7

2*5 volumes of 70 per cent, alcohol instead of I'O volume required
by water-distilled oils recorded by Scliimmel c& Co.

Gcmniol

Serial No,

Combined,

Free.

Total.

1 .

12-1

76-36

88-46

2 .

13-55

I 69-98

83-33

3 ! !

8-67

68-23

4 .

8-48

83-15

The Sofia or gingergrass oil has quite different characters from
those above described. They are as follows : —

Specific gravity . . . 0-900-0-955

Optical rotation . . . — 30° to -f- 50°

Refractive index . . . l*4:780-l-4950

Acid value .... 2-6

Ester value .... 8-55

Ester value (after acetylation). 120-200

The oil is not always soluble in 3 volumes of 70 per cent, alcohol.

Pahnarosa oil {Moiia) contains as its principal constituent free
geraniol, together with some geranyl esters. IMethyl-heptenone
and dipentene are present in traces, and possibly farnesol (Elze,
CJiem. Zeit., 1910, 34, 857).

Gingergrass oil {Sofia) contains the terpenes dipentene, limonene,
and phellandrene and, in addition to geraniol, periUic (dihydro-
cumic) alcohol Cio HjgO. Carvone is also present, and an aldehyde,
^10 HioO, of specific gravity 0-935, not yet characterised (Walbaum
and Hiithig, ScIiimmeVs BericJit, April, 1904, 52 ; October,
1904, 41 ; April, 1905, 34).

Although the world’s supply of these oils is produced by India,
samples of oil of the Motia type have been distilled experimentally
in Java and examined by Scliimmel cO Go. {Bericht, October, 1914 ;
April, 1915). These oils were of exceedingly liigh grade, and
accentuate the need for an improvement in the Indian production.
Their characters were as follows : —

Specific gravity
Optical rotation
Acid value
Ester value .

Ester value (after acetylation)
Total geraniol

0- 891-0-892

+ 0° 30' to + 0° 42'

1 - 2 - 1-8
37-5-51-6
273-277

94-3-96 per cent.

278

PER F V }! K R Y

Both oils are used as perfumes, especially for soap. Palniarosa
oil is also used for the separation of geraruol {q.v.). The oils are
exported in “ pots ” containing up to 250 Ih. of oil.

GLOBULOL. — ^This body is a crystalline sespuiterpene alcohol
which has been isolated from the oil of Eucahjpius globulus by
Smith. It is a cr 3 'stalline substance melting at 88° to 89°, of
characteristic eucalyptus odour.

GLYCERINE. — Gtycerine is not a raw material of perfumery,
but is used to a fairly considerable extent as an accessory to the
perfume industry, so that a short description of it is not out of
place. Glycerine is a trihydrlc alcohol of the formula C 3 Hs(OII) 3 ,
in which the hydroxjd groups can react with acids to form esters,
so that three esters are possible "ndth any monobasic acid, according
to whether one, two or tliree hydroxjd groups have reacted.
Gtyceiine is used to a considerable extent in certain types of face
creams, etc., and should, for this purpose, be of a high standard
of piuity. Eor all practical purposes, it may be said that the
world’s supply of glycerine is derived from the saponification of '
animal or vegetable fats, which consist of the glyceryl esters of
the liigher fatty acids, such as oleic, stearic, and palmitic acids.
The teclmique of fat splitting is outside the scope of this work ;
for detailed information in regard to it, standard works on soap
making, etc., should be consulted.

Gl 3 ’’cerine is a colourless and hygroscopic liquid, existing in a
state of superfusion, since when cooled to a very low temperature,
it sets to a erj-staUine mass, especially on continuous agitation,
or by infecting it with a ready formed crystal. When so crystal-
lised the crystals melt at about 17°. The specific gravity of pure
liquid glycerine is about 1*264, decreasing by the addition of
water. Commercial gtycerine always contains a little water, and,
in its highest degree of concentration, is sold as of specific gravity
1*260. In the anatysis of glycerine the following points should be
taken into account : —

(1) Colour . — ^This should, for perfumery purposes, be water
white.

(2) Odour . — ^High grade gtycerine should be practically
odourless.

(3) Ash . — ^This should be very low, certainly not above 0*25
per cent.

(4) Strength . — Not more than 2 per cent, of water should be
present.

The following table of specific gravities gives the strength of

270

P E B F U 31 E B Y

pure glycerines, that is, glycerine in which the onty foreign
substance present in more than traces, is water. In the case of
crude glycerine, other methods of determining the strength must

be used : —

Glycerine present

Specific

Per cent.

gravity.

100

. 1-2640

. 1-2612

. 1-2585

. r2660

. 1-2532

. 1-2505

. 1-2480

Glycerine present Specific

Per cent. gravity.

93 . . 1-2455

92 . . 1-2427

91 . . 1-2400

90 . . 1-2375

86 . . 1-2242

80 . . 1-2112

Glycerine can be obtained by fermentation, but the process is
not yet in a position to compete with soap makers’ gtycerine, but
as fermentation glycerine is almost certaui to be of technical
importance in the near future, it may be dealt ■u'ith briefly. The
following details are due to K. Schweizer {Helv. Ohim. Acta, 1919,
2, 167 ; andP. cO E. 0. B., 1919, 151).

As early as 1857, Pasteur {Gompfes Benelux, 1857, 45, 2, 1913),
in the course of his classic researches, had found that during
alcoholic fermentation glycerme was formed as a by-product ; he
obtained a yield of 3-60 to 3-64 per cent, on the sugar fermented.
Later, Laborde showed that the amount of glycerine formed varied
according to the quantity and species of yeast employed, and
might reach as much as 7-76 gi-ams glycerine from 100 giams
sugar. The quantity of glycerine obtained depends also on the
conditions under which the yeast grows ; in a medium rich in
nutritive matters more is obtained than m a medium less favour-
able to the growth of the yeast. It has further been observed
that the production of glycerme does not depend on the formation
of alcohol, and is in no way proportional to the latter.

P. Ehrlich considered that this trfliydric alcohol might origmate
from certain ammo-acids, as is the case with amyl and other
alcohols. It has also been supposed that it is formed from the fatty
substance found as small liquid drops in the yeast cells ; but
Buchner and Meisenlieimer {Berichie, 1910, 43, 1782) showed that
the quantity of glycerine formed was much greater than that
corresponding to the free fatty acids involved, and hence con-
cluded that the glycerine of fermented liquids must have another
origin. Oppenheimer in 1914 proved that glycerine could be
produced by reduction of glyceric aldehyde and of dihydroxy-
acetone ; now these two substances are formed during alcoholic

280

PEBF U MER Y

fermentation, and indeed, according to some hypotheses, are
intermediate products in the conversion of sugar into alcohol.
It seemed possible, therefore, that by acting upon these com-
pounds by a reducing agent at the moment of formation, they
could be ehminated from the fermentation cycle in the form of
glj'cerine.

The greatest difficult}^ was to find a species of yeast which
could live in the presence of large amounts of salts, yeasts being
usually very sensitive organisms. This difficulty was only over-
come b}’ using a commercial pressed yeast prepared with molasses,
which gave satisfactory* results. It was necessary at the same time
to find a reducing agent wliich would not present the gro%vth of
the yeast.

For the study of acid reduction Schweizer made the following
experiment : After having sterilised a solution of 64 grams of
saccharose in 200 c.c. of water, he added 1 gram of ammonium
sulphate (to supply the nitrogen necessary for the growth of the
yeast), and 26 grams zinc powder as reducing agent. After
making the mixtm’e feebly acid with dilute sulphuric acid, ho
fermented it vith 6 grams of pressed yeast. During the whole of
the fermentation the mixture was kept shghtly acid, and the
temperature was not allowed to fall below 25°. An analysis at
the end of the fermentation gave : —

Sugar . . .32 per cent.

Acidity . . 20c.c.neutrahsed 0'26c.c.normalNaOH.

Soerensen number. 10 c.c. corresponded to 3-6 c.c. N/10

NaOH.

The initial temperature was 27-5°, but after six hours it had
fallen to 25°, and the yeast had not grown appreciably. With a
view to assisting the growth, he added 0-5 gram of ammonium
hydrogen phosphate, OT gram of magnesium sulphate, and a trace
of potassium sulphate. The following figures were then
obtained : —

Sugar . . .32 per cent.

Acidity . . 20 c.c. neutralised 0-28 c.c. normalNaOH.

Soerensen number. 10 c.c. corresponded to 3'S c.c. N/10

NaOH.

It was ten hours before the fermentation commenced, slowly*,
without becoming energetic even after twenty-four hours.

The fermentations under these and similar conditions were very
incomplete, and it was necessary’- to abandon reduction in an acid
medium.

2S1

P E B F r il/ E R y

Yeasts cannot live in an alkaline inedinm, and it remained,
therefore, to attempt the reduction in a medium kept as neutral
as possible. These conditions are fulfilled, hj’’ the use of sodium
sulpliate in the presence of powdered chalk. Tor example,
04 grams of saccharose were dissolved to give a 14 per cent,
solution, to which, after sterilisation, were added 0-1 gram
ammonium sulphate, Od gram of ammonium hydi’ogen phosphate,
0-1 gram of magnesium sulphate, and finally some powdered
calcium carbonate. The mixture was fermented Avith 0 grams of
yeast, the temperature being kept at about 30°. The yeast
begins to develop after four hom’s. J\Ieanwhilc, a solution of
10 grams sodium sulphite, 0-8 gram ammonium sulphate, and
0-8 gram ammonium h3^drogen phosphate in 120 c.c. of Avater was
prciDarcd. EAmry half hour 5 c.c. of this solution AA'ere added to
the fermenting liquid, until all had been introduced. A very good
fermentation resulted, Avhich was complete in tAvo days. In spite
of the chalk, there Avas produced an acidity of 0-G c.c. N-acid per
20 c.c. liquid.

Having thus discovered a suitable reducing agent, the influence
of concentration on the course of the fermentation AA'as studied,
and for this the folloAA’ing solutions Avere used : —

(1) Sugar solutions 20 per cent, and 5 per cent.

(2) HutritiAm solution ; 2-5 grams ammonium sulphate, 2-5
grams ammonium h 3 ’'ch’Ogen phosphate, and O-S gram magnesium
sulphate ; dissolved in Avator and diluted to 300 c.c.

(3) Reducing solution : 17 grams sodium sulphite in 100 c.c.
Avater.

Each solution Avas sterilised by heating on the AA'ater bath
during a night, and, after cooling, 5 grams of j’east were added for
each experiment.

A. — 20 per cent. Sugar Soluiion.

Time.

Per cent.
Sugar.

Temperature.

Xutritivo

solution.

Reducing

solution.

1st daj’’

18-9

22°

30 c.c.

20 c.c.

2nd „

3rd „

12-8

25°

30 „

4th „

6-6

26°

25 „

20 „

5th „

3-9

25 °

30 „

25 „

6th ,,

4-3

26°

282

PE EF U 31 E E Y

Tims, in all there were added llo c.c. nutritive solution and
95 c.c. reducing solution for an initial volume of 500 c.c., which
had increased by the sixth day to 670 c.c. The growth of the
yeast was not vcr}' rapid. The gl 5 'cerine was determined by the
method used for its estimation in wine ; 100 grams sugar gave
4*5 grams glycerine.

B. — 5 per ce7it. Sugar Sohtdon.

Time.

__ . _

Per cent.
Sugar.

Temperature.

Nutritive

eolution.

Rovlueing

Folution.

1st daj'

4-9

22°

20 c.c.

2nd ,,

I ““ ^

—

3rd ,.

2-3

25°

30 „

4tli

3-8

26° i

25 „

20 „

5th .

4-2

25° i

The sugar was determined, as in the previous experiment, by
Balling’s saccharimeter. The density of the liquid had increased,
owing to the salts added and the fermentation products. The
nutritive solution added was 85 c.c. in all, the reducing solution
70 c.c. The growth of the yeast was fairty good, but was much
slower by the fourth day. The volume, initially 500 c.c., increased
to 630 c.c. While the more concentrated sugar solution gave
0-67 gram glycerine per 100 c.c., the dilute sugar solution was
found after fermentation to contain 0*32 gram gl 3 'cerine per
100 c.c. The 3 'ield is thus 8-0 grams gtycerine from 100 grams
sugar. High concentration is therefore unfavourable to the forma-
tion of the trihj'dric alcohol.

But j-iclds of this order are obtainable bj’’ simple biological
processes in the absence of any special reducing agent. It was
therefore necessary to make new experiments in the presence of
larger quantities of sulphite. To this end 40 grams saccharose,
2 grains ammonium lydrogen phosphate, and 1 gram dipotassium
phosphate were dissolved in 400 c.c. water, and the solution
introduced into Haj-duck’s apparatus for the determination of
the fermentative power of yeasts. Having added 10 grams pressed
j-east, the fermentation was allowed to become appreciable, and
then 30 grams sodium sulpliitc were added. After twenty-four
hours the fermentation was finished. An intense odour of Vanillin
was given off by the solution. The COg evolved was about

283

TEBFUMEBY

800 C.C., and 100 grams sugar had given 21*30 grams glycerine
(mean of several experiments).

Certain biological reactions of j’-east are accelerated by the
presence of oxygen, and it appeared of interest to discover whether
that were the case with this fermentation. As in the preceding
experiment, there v'cre introduced into a Hayduck’s apparatus
a solution of 50 grams saccharose in 600 c.c. water, and 10 grams
pressed yeast, 30 grams sulphite being added in three portions ;
1,820 c.c. COg were evolved, and the fermentation, without
aeration, was finished in twenty -four hours. The final volume
was 520 c.c., and a determination of the glycerine present gave
9-36 grams, corresponding to a yield of 18-72 grams from 100
grams sugar.

An exactly similar experiment was performed in a wash-bottle,
into which was passed a ciu-rent of sterilised air. After the fer-
mentation the volume of liquid was 630 c.c., and the amount of
glycerine 0-75 per cent., corresponding to a jdeld of only 9*44
grams glycerine from 100 grams saccharose. Without aeration,
therefore, twice the amount of gl 3 ^cerine is obtained. This result
was to be expected, since aeration favom-s oxidation, and thus
prevents the reduction of the gtyceric aldehj^de and the dilij’--
droxyacetone.

It was by this sodium sulphite method that glycerine was
prepared on a commercial scale during the war by certain
belligerent countries.

GLYCERYL ACETATE. — Gtycerine C 3 Hg(OH) 3 , being a
trihydi’ic alcohol, forms three acetic esters ; glycer 3 d monoacetate
{monacetin), gl 3 "ceryl diacetate {diacetin) : and gl 3 ’-ceryl triacetate
{iriacetin). Frequently the triacetin of commerce contains some
of the other two esters. This substance has no legitimate use
in perfumer 3 '', but is often used as an adulterant of ester-
containing oils, such as bergamot oils. For its detection, see
“ Esters, Artificial, Detection of.”

GOLDEN ROD OIL. — ^Various species of solidago, of which
the best know is Solidago odora, yield up to 1 per cent, of an
odorous essential oil contaming up to 75 per cent, of rheth 3 d-
chavicol. The oil has a specific gravity 0-937 to 0-960 ; optical
rotation, 7° to -j- 14° ; refractive index, 1*5050 to 1*5160 ;
ester value, 6 to 10 ; and ester value after acetylation, 18 to 25.
The oil known as Canadian golden rod oil is the product of Solidago
Canadensis, and consists almost entirely of terpenes. The oil has
little value in perfumer 3 ^

284

PERFU 21 E R Y

GOUFT, OIL OF. — ^The Algerian plant Arlemisia cam-
2 )estris, var. odoratissirna, jnelds an essential oil ■vrhicli is known
locally as oil of gouft. It was originallj’- examined by Jeaneard
and Satie {BiiU. Soc. Cliim. (3), 1904, 31, 478), and later by
Rourc-Bcrlrand Fils {Bulletin, 1920, 4, i., 27). It is an odorous oil
containing geraniol, gerain'l acetate, and pinene (probabty also
nopinene). The follo^ving are the characters assigned to it by the
investigators mentioned ; —

Jeaneard and Satie.

Roure-Bertrand.

Specific gravity

0-872 at 9-5°

0-8763 at 15°

Optical rotation

— 15° 20'

— 16°24'

Acid number ....

1-12

0-94

Ester number

12-88

29-87

Saponification number
Saponification number (after

30-81

acetylation)

41-07

Total alcohols as geraniol

11-9 per cent.

11-65 per cent.

Free alcohols as geraniol

8-36 „

3-44 „

[Note that the table of characters on page 291 of Volume I. of
the writer's work, “ The Chemistrj’’ of Essential Oils, etc.,”
4th edition, are assigned to this oil through the accidental mis-
placement of the last two lines on page 290. Tliis table belongs,
in fact, to the oil of Artemisia herha alba, var. genuina, “ Scheih
Oil.”]

GRAINS OF PARADISE.— Grains of Paradise are the
pungent aromatic seeds of Amomum Melegueta, a plant allied to
ginger ; the seeds have an odour recalling that of galangal. It
is possible that other species of amomum are used for the
collection of these seeds. The plants are natives of West Afriea,
where they are more or less cultivated, and are also found in the
wild condition. The seeds, which were at one time known as
2Iclegetce, owe their name to the native name, corrupted from
“ JIalaga,” meaning “ pepper,” or possibly to the word Melle,
the name of an empire in the Niger country, which maj' itself
have the same origin from “ Llalaga.” These seeds are also known
as guinea grains or melegueta pepper. It is not an injurious drug,
but in the reign of George III. an Act was passed forbidding any
brewer to have it in his possession or to use it in making beer,

2S5

PERFUMERY

tinder a penalty of £200 ; and forbidding any druggist to
to a brewer, under a penalty of £500.

The seeds yield from 0*3 to 0-75 per cent, of essential oil,
a specific gravity about 0-894 ; optical rotation about
and refractive index, 1-4912. Its ester number is about 40,
ester number after acetylation about 64. Its constituents
not been investigated.

GRASSES (PERFUME) OF INDIA AND CEYLON
There are a number of oil-yielding grasses found in India
Cejdon, and, to a smaller extent, some of them in the Ma.
Peninsula, Java, and other places, whose essential oils are of th
highest importance to the perfumer. Some of them have no
yet been exploited commercially, and may have considerab-
value when they are more available to the perfumer. All of these
belong to the tribe Andropogoneos, which is very rich in aromatic
species. All of those which yield essential oils obtainable in
commerce wfil be found described under their respective headings,
such as “ CitroneUa Oil,” “ Gingergrass Oil,” “ Lemongrass Oil,”
“ Vetivert Oil,” etc. There has, however, been a complete
re-examination of the botanical relationships of these plants by
Dr. Stapf [Kew Bulletin, No. 8 of 1906), so that the following maj’
be accepted as the present state of our knowledge on this subject : —

According to Stapf, the aromatic character of some of these
grasses is so pronounced as to have attracted the attention of
man at a very early period of his history. They found a place
in the performance of religious rites, among domestic medicines,
in the dispensaries of the medical practitioners, and in the
department of spices and perfumes. The Schoenantlius of the
Ancients, the Viranam of the Vedhas, and the Sereh of the
Malays are illustrative instances, and there is very little doubt
that the much-discussed Kalamos arotnaiikos of the Greek writers
was a plant of the same category, although we have not so far
succeeded in fixing the species. With the discovery of more
powerful or more pleasant aromas these oil-grasses gradually lost
their importance or even fell out of use. But in our own day
the highly perfected art of perfumery has seized on them again,
has revived the taste for their odours, and created that demand
for their oils which has found its response in the development
of a regular oil-grass industry in Ceylon, India, and to a less
degree in the Malay Peninsula and in Java. Out of the twelve
grasses described here, the genus Gymbopogon claims ten, and
Vetiverm and Andropogon contain one each.

286

PE nr u 31 E R }■

(1) Cymhopogon Schosnantlnis was the Andropogon Sclw:nanthus
established by Linnasiis in the first edition of liis “ Species
Plantarum ” in 1753. This plant is knoma as camel grass or
izhhir (Arabic), or hliavi (Hindustani). As it is the Hcrha
Scltccnantlii of the ancients and the foundation of the species, the
following history, due to Stapf, is of interest : —

When in 1881 Emil Brugsch Be}'’ discovered the tomb of
Dcir-el-Bahari in the necropolis of Thebes, the secret vault which
contained the coffins of so many illustrious kings also yielded a
remarkable profusion of botanical treasures : funeral VTeaths
which the Icings of the Twentieth or Twenty-first D}masty (be-
tween 1200 and 1000 B.c.) had deposited on the sarcophagi of their
predecessors, offerings of fruits, lichens, bundles of a grass {Desmos-
iachya hipinnaici), and quantities of the straw of another grass,
which Professor Schweinfmrth recognised as Gymnanthclia lanigera
(a rarely used sjmonym of C. SchosiiantJms). Some of the in-
florescences were still in excellent condition. Even “ the odour
of the grass was preserved to a certain extent in the mixture of the
offering.” So early begins the history of the grass. Then the
grass was found under similar conditions in the tombs of the
cemetery of Hawara, in the ra}nim, again associated with Desmos-
iachya bipinnaia. According to Professor Flinders Petrie, some
of the tombs were probably of the Twentieth, Twenty-sixth, and
Thirtieth Dynasties, but most were Ptolemaic. According to
Loret, the grass is also frequently mentioned in hieroglyphic
perfumery recipes as “ Aetluopian cane,” “ rush of the Sudan,”
and “ C}’perus of the West.” Whether all of these names actually
refer to C. Scliapianthus or not, the finds of Deir-cl-Bahari and
Hawara afford, in any case, indisputable proof of tlie high place
which was assigned to the grass 3000 years ago. To-day
C. SchccnanfJnis does not grow in the neighbom-hood of .old
Thebes or in the ra}mm ; it has, in fact, vdth one exception,
never been observed in the Nile Valley north of the Baiuda
Desert (16° to 18° N.), the exception being some specimens
collected by Bove in the desert near Cairo in 1829. Schweinfurth
identified the Andropogon of Deir-el-Bahari more particularly
with the article which nowadays is brought down from the Sudan
and sold in the bazaars of Cairo as a medicinal drug under the
Arabic name mdharch.

It has been suggested that the EcineJi bosetn or Kanch hailobh,
the “ good ” or “ fragrant ” reed of the Bible, was also C. Schcc-
7ionfJn!-s. It may, of course, be assumed that the old Hebrews

2S7

PERFUMERY

knew the grass ; but how far it answered to those terms is difficult
to say, considering the vagueness of the passages in which they
occur. It was known to Hippocrates under the name Schomos,
under which name it was often used in medicine. It is quite in
keeping vdth the general character of Greek and Roman literature
that one does not meet with any serious attempt at describing
the herb schoinos. In fact, the only reference to it wliich con-
tains a descriptive element is in Dioscorides, where he gives
instructions for the selection of the material : it is to be fresh,
reddish, many -flowered, purplish and whitish ..when spht apart
{i.e., when the leaf bases, which are purphsh and wliite, are
pulled apart), to emit an odour lilre roses when rubbed in the
hand, and to have a hot, pungent taste. The use of the drug
continued in the West after the downfall of the Roman Empire,
although apparently only for medicinal purposes, through the
Middle Ages, and even into the eighteenth century, when it
gradually became obsolete. We And it in the prescriptions of
Aetius (a.d. 450 ), and in the writings of the School of Salerno.
Here the name Palea camelorum may have originated. At least
it is attributed to Matthasus Platearius (about the middle of the
twelfth century) in the various editions of the “ Ortus Sanitatis,”
although it may, of course, be much older, as Galenus had already
connected the Sclicenanthus with the camel. In the “ Ortus
Sanitatis ” we also And the flrst flgure mtended to represent the
Schosnantlms or Sqitinanthus, as it is called there. It is so con-
ventionalised as to be umncognisable. Erom Brunfels (a.d. 1536 )
onward it is a standing article in aU the herbals of the sixteenth
and seventeenth centuries, and is the subject of sometimes
elaborate discussions in the commentaries on Dioscorides, Plinius,
and Theoplnastus. It was very frequently flgured in those works,
the flgures behig drawn from the mostly barren leaf tufts as they
reached Europe. Sometimes inflorescences more or less con-
ventionahsed were added. One of the earliest of those flgures,
by Lobel (a.d. 1576 ), is among the best. A very good description
of the drug was given by Job. Bauhin (a.d. 1658 ). Einally, in
1692 , we have Plulcenet’s description and figme. Both are
indifferent ; but they are supported by Plul^enet’s original
specimen, which still exists in his herbarium at the British
Museum, and is the typical ScliosnantJms of the old herbalists.
On this, and on this alone, Linnaeus based the Lagurus of his
“ Materia Medica,” which is the backbone of the Andropogon
Sclicenanthus of the “ Species Plantarum.” The Nabataean Schce-

288

PEBFU ME RY

nanilivs vras, in tlie times of Dioscorides and Plinius, more valued
than any other. It was called Nabataean more lilcely because
it came rid Nabataja than on account of its growing there. In
connection with this, it is interesting to note that, according to
Me\-er, Qutsami’s “ Book of Nabataean Agricultiu-e ” actually
enumerates Idshir {Izkhir, the Arabic name of Sclmnantlms, qua
drug), but with the epithets “ Babylonian ” and “ that of Hedjas,”
and not as Nabataean. Mej’cr quotes from Ibn Alawwam’s “ De
Agricultura,” who in turn quotes largely from the Arabic trans-
lation of Qutsami’s work, which was probably vvitten in the
second or tliird century.

Isliag Ben Amran of Bagdad (died a.d. 903 or 905) mentions
the Hedjas as the country producing the best Izkhir. It comes
next to that of Antiochia, ' wliilst the African is the worst. The
Izhhir of Antiochia is evidently the “ Babylonian ” variety,
Antiochia being merely the market whence it was distributed.
Avicenna (a.d-. 980-1037), too, distinguishes two kinds, the
Arabian and an inferior “ foreign ” {ajami) kind. As may be
expected, there is more freedom in the way in which the Arab
•nwiters treated the subject, as some of them must have known
the gcass in the field, or, at any rate, had first-hand evidence.
Thus Abu Hanifadt (died a.d. 895) gives a description of it
which could only have been made from autopsy : “ Izhhir is a
plant with a root deep down in the ground and slender, very
fragrant culms, like rush or papyrus, but finer and with smaller
joints. It has tufted infructescences (fruits) like the panicles of
the reed, but more delicate and smaller. It is pounded and
mixed vdth perfumes. It rarely grows solitary. Where it has
settled, it may be seen to spread and cover the ground ; it inhabits
plains and desert land. When it dries up, it turns white.” Like
the old Greek doctors, the Arabs prescribed it for the preparation
of unguents, theriacs — among them the famous Elecluarimn
Mithridatis — and oils. Ibn Baithar quotes from the “ Books of
Experience ” the method of preparing the latter, thus : “ Take
of the fiowers of the grass, put them in double the quantity of oil
of unripe olives . . . press the whole well and throw the fiowers
away ; take another lot of fiowers and put them in the oil. Repeat
this three times in the hot season.” From the Arab vviters the
drug passed naturally into the Persian pharmacopoeias, as, for
instance, the “Ulfaz Udwiyeh” of Mohammed A' dullah Shirazi
(a.d. 1450), and the “Pharmacopoeia Persica” of Prater Angelus
(a.d. 1681). YiTience the Persians got their supply of Izkhir is

V 23a 10

PERFUMERY

not quite certain. So far tlie grass lias been found only in a few
localities in Persia, and nowhere in quantity. It was probably
mostly Arabian. Still Kaempfer speaks of a Persian and an
Arabian SchcenantlmsP Considering the part which Arabian and
Persian doctors played at the courts of the Mahometan princes
of India, it would be surprising if the ingredient of so many
theriacs, electuaries, and other preparations had not also found
its way into the Indian dispensaries. W^e possess a fairly full
account of an instance of import of IzlcMv under rather remarkable
cii'cumstances in Garcia de Orta and Acosta. This is what Orta,
in Clusius’ edition of the Aromata,’’ says : J^incus odoratus
gi’ows in great abundance in the Ai’abian provinces of Mascat and
Kalhat. The natives call it Sctchhar^ some also Hcixis ccicJiulc
{JicisJiish gliusuV)^ that is, lotion grass . . . and the flowers Focci,
. . . With the Indians no special name has arisen ; but they
dub it Mascat grass, some also Mecca grass, and also camel hay.
There are in those countries plenty of asses, mules, horses, etc.,
which know no other fodder. ... It is imported into India for
medical purposes ; but the greatest quantities come with the
horse dealers (of j\Iascat and Kalhat), who take it tied up into
bundles with them in their ships to use it as litter for their
horses. ... I remember that at Din they sold many bundles of
Jiincus for a mere trifle . . . but the natives do not appreciate
it, as they are a rough and savage people, and they do not use
it.. We, however, and the Arab and Persian doctors employ it.’’
The influence of the Persian phj^sicians and the reputation of
their pharmacopoeias were sufficiently weighty also to transfer
the foreign name, Izichir, to the native drug. Not only was, and
still is, the G. Schceiianthiis of the Panjab sold in the bazaars as
IzIcJiiv, but the name has also passed on, with or without the
qualifying epithet, ajami (foreign) ov Hindis to V etiveria zizanioides
(A, Tnurioatus) and other indigenous aromatic grasses, so that it
has become with certain writers almost a generic name. Thus
the Izlchir of the Abir IzJchir of the Ain-i-Akbari (end of the
sixteenth century) is F. zizanioides ; the Taleef Sherif ” has
gundheel {0. Martini) as synonymous with Izlchir^ and the author
of the ^ Makhzan-ehAdwiya ” (a.d. 1771) enumerates no fewer
than six Hindi synonyms for Izlchir^ most of them vernaculars
of G. Martinis It will be seen that the vernacular synonymy of
G. Schcenanthns was, in India at any rate, just as confused as
the scientific nomenclature of the species was up till recently.

(2) Gyivho'pogon Iwarayicusa . — ^This gra^s first became known

290

PER F U JI ERY

tliroiigh a piil)Iication on the Kardns Indica, or spikenard, in 1790
by Blanc, avIio gives the following account of its discover 3 ' b3>-
his brother : —

Travelling with the Xabob Vizier on one of his hunting
excursions towards the northern mountains, I was surprised one
da 3 ', after crossing the Eiver Rapt 3 ', about twent 3 ' miles from the
foot of the hills, to perceive the air perfumed witli an aromatic
smell ; and. on asking the cause, 1 was told it proceeded fronr
the roots of the grass that were bruised or trodden out of the
ground b 3 ' the feet of the elephants and horses of the Nabob’s
retinue. The country was wild and uncultivated, and this was
the common grass which covered its surface, growing in large
tufts elose to each other, veiy ranlc, and in general from 3 to
4 feet in length. As it was the winter season, there was none of
it in flower. Indeed, the greatest part of it had been burned
dovm on the road w'e went, in order that it might be no impedi-
ment to the Nabob’s encampments. I eollected a quantity of
the roots to be dried for use, and earefull 3 '- dug up some of it,
which I sent to be planted in my garden at Lucknow. It here
throve exceedingly, and in the rain 3 ^ season it shot up spilces
about 6 feet high. ... It is called by the natives Teranhus,
which means literally in the Hindu language ‘ fever restrainer,’
from the virtues the 3 ’- attribute to it in that 'disease. ... It is
esteemed a powerfrd medicine in all kinds of fevers, whether
continued or intermittent. The whole plant has a strong aromatic
odoiu ’ ; but both the smell and the virtues reside principall 3 ^ in
the husly' roots, which in chewing have a bitter, warm, pungent
taste, accompanied with some degree of that kind of glow in the
mouth which cardamoms occasion.”

It was believed to be the spil^enard of the ancients, but this
is probabl 3 ' not true. The spelling of the name vlth an “ i ”
obscures its derivation, which is from jti-am (fever) and anhusa
(the hook used by elephant drivers to restrain their elephants).
The name thus means “ fever restrainer.”

(3) Cymlopogon Nardns . — This grass is that producing the
well-known citronella oil. Early botanists believed it to be the
Nardns Indica of the ancients, so that Linnasus gave it the name
Avdrojwgon Nardvs.

The citronella gi-ass early shared the fate of the other aromatic
Andropogonco: by becoming almost hopelessl 3 ' confiLsed. It was
Ainslie who first (1813) suggested that it was identical with the
“ gingergrass ” of Courtallam {G. jlexnosits) and tlic cultivated

201

10—1

PE UFU MBliY

“ lemongrass ” [ 0 . ciimtus), and it seems to have been known for
a long time loy the latter name ; hut as “ lemongrass ” was very
generally put dowm as Andropogon Scho&nantlms, eitronella was
also frequently referred to by that name, ehiefly by pharmacists
and chemists. Then, the French name for “ lemongrass being
citronelle, the latter term also found its way into English literature,
origmally as a synonym of “ lemongrass ” in the wider sense, and
later on more especially of the “ Ceylon lemongrass,” that is,
G. Nardus. Perema (1850) seems to have been the first to use
the term “ citronelle oil ” as equivalent to “ lemongrass oil.”

J. Bell, in his notes on the London International Exhibition
of 1851, mentions “ oil of cintronelle, or oil of lemongrass.” He
stated that it v^as imported from India, " and is the produce of
a grass known to botanists as Andropogon ciiraium, and by some-
persons considered to be identical with Andropogon SchmnanthusP
In the Ceylon Catalogue of the Parish Exhibition of 1855, p. 17,
we find two distinct oils : (1) lemongrass oil, from A. Schce-
nantlms, and (2) “ eitronella oil ; citron oil ; perfumery,” and
agauist the latter there is in the Kew copy an entry in Alex.
Smith’s handvTiting: “ Citronella oil, AndroptogonP W. S.
Piesse, in his “ Art of Perfumery,” 1855, p. 31, also refers to
“ eitronella,” sajnng : “ Under tins name there is an oil in the
market, chiefly derived from Ceylon and the East Indies ; its
true origin we are unable to decide. In odour it somewhat
resembles citron fruit, but is very inferior. Probably it is procured
from one of the grasses of the Andropogon genus.” Gladstone
(1872) and C. H. A. Wright (1874) were the first to examine, under
the name of “ citroneUa,” the oil of G. Nardus, as is evident from
then descriptions of the oil, but both referred it to Andropogon
SchcBnantJms. Even as late as 1880, it was confused with G.
flexuosus and G. ciiratus by Bentley and Trimen, who figured a
specimen of the former as Androptogon Nardus. In 1883
“ eitronella ” was at last clearly confined to Androjiogon Nardus
by Watt, who gives the average exportation of eitronella from
Colombo as amounting to about 40,000 lb. ; the exact return for
1864 was 622,000 oz.

Outside Ceylon A. Nardus has been in cultivation for some
time in Penang, whence eitronella oil is mentioned as early as
1872 by Gladstone, and in the Straits Settlements and Java.
When it was introduced into the Malay Peninsula and Java is
uncertain, but it cannot have been very long ago. McNair, in his
book, “ Perak and the Malays,” 1878, p. 73, speaks of “ the

292

PERFU jfE 7?

iloiiri-'lunir growth of cilronclle and lemongra.-^?, from which
o'-^cnti.d oil*^ are extracted, as worth mentioning t but in 18S0
C.*Uul'*y complain^ of the insufficient attenlioii which the cultiva-
tion of tliC'^c two grasses receives in the Straits, and in 1000 the
total area of citronclla estates in the peninsula was estimated at
only acres at the liighest. In Java it is mentioned by

Itoin burgh in IS 02 as Pocmpoc! .‘^axh ivangi under A, Jirarancvsci,
and is staled to have been introduced into tlic Cultuurtuiii
in ISOL He drew tlie attention of Scliiinmel & Vo, to tlie oil
])ropared from the Javanese crop : this reference event ualh" led
to tlie establishment of citronella distilleries in Java. According
to Gildemcister and HofTmanii, both the Mala^’ Peninsula and
the Java grass rci^rescnt the Jllaha Pengiri variety (sec below).
Quite recenth" experiments in growing citronella grass have been
made in the West Indies.

Two kinds of citronclla grass have recently been distinguished
b}^ the growers : il/a//a Pengiri (the Great Pengiri), and Lenabedu
or Lana Batii Pengiri, or, briefly, LenahaUi, The former is also
known as “old citronella grass,’’ or “Winter’s gi*ass,” because
it is now almost exclusively grown hy Messrs, Winter & Son ; the
other is spoken of as “ new citronclla grass.” Specimens of both
varieties received at Kew from Galle, so far as they go, do not
show any moriffiological differences. The old citronclla grass is
described as a surface feeder, which soon grows out of tlie ground
and gets exhausted, dying off after ten or fifteen 5 'ears of cultiva-
tion : and it has somewhat broad leaves, and tlie bushes formed
are larger than the second (i’.c., Lenahatu), It fields a finer oil,
but the necessit}’' of freq^uent replanting has led to its being more
and more replaced by the Lenahatu variety".

6 b Kerdns in its t 3 ’pical form is onlj* known in tlie cultivated
state. It is an auTiless gi'ass, the valve or flowermg glume of the
hermaphrodite spikelet being either entire or more or less bifid,
with a minute point or a very^ fine and short bristle from the sinus.
The flower.s are usually apparently normal, but do not seem to
set freely, and in some cases all the spikelets are male or otherwise
im])erfccl]y developed, or they' are infested with Usiilcigo, On
tlie whole, the reproductive sy^stem seems to be debilitated. This
is tlie case with all tlie specimens I have seen, irrespective of their
origin, and is evidently' the result of the treatment the grass has
experienced from the grower, in whoso interest it is that they'
should not flower, as, according to Gildemcister and Hoffmann,
“ otherwise tlie tufts become too dense, become yellow uitlun.

203

PEBFU MERY

and spoil.” Stil], a certain amount is allowed to seed for renewing
the plantations, the nsual mode of propagation being apparently
b}’’ dividing the bushes. The reduction or suppression of the awn
is no doubt in correlation vith tlie partial sterility of the cultivated
C. Nardvs, the wild ancestor of v'hich we have to seek among the
awned forms. It has very generally been assumed that the
citronella grass is a descendant of the wild Mcma grass of the
Ceylon Patanas, but it is unfortunate that there is no specimen
at Kew which is definitcl}’- stated to have been collected in the
wild state. Sir Josej)!! Hooker, however, vlio had the grasses of
the Peradoniya herbarium at his disposal when working out the
GrammecG for Trimen s “ Handbook of the Plora of Cej'^lon,” says
that there wore three specimens of the wild Mc7?i(2 in that collec-
tion from Galle, Mao 3 ’a, and Peradenij'a, and thej’- were all
Hackcl’s AndrojJogon Nardus, var. nilagiricus. Willis also states
that the Manu of the is distinct from the cultivated

citronella grass, but docs not sa}' how it dilYers. Now there is a
Hew a suite of excellent specimens of the cultivated awnless
0. Nardus from I\rr. Jowitt’s estate at Bundarawalla, and, sent
with them at the same time and from the same localiCv, and
numbered concurrently with the first, is another set which is
undoubtedly Andro 2 )ogon A^ardus, var. mlagiricus. Whether
thej’- grew wild on the estate or Averc in cultivation is not stated.
A careful comparison of both sets has convinced mo that this
Andropogoii Nardus, var. mlagiricus, is, as »Su’ Joseph Hooker
has stated, actuall}’- the mother plant of the Peugiri Aland, or
citronella grass. Gildomcistor and Hoffmann state, on Mr.
Winter’s authoritj’-, that the AlaJia Pengiri came from jMalacca.
As the citronella grass is a comparative^ recent introduction to
the Malay Peninsula, and certainly does not occur there in the
wild state, this can onty mean that it has, possibty as an improved
race, been reintroduced into Ce 3 don from ]\Ialacca ; but, as the
Alaha Pengiri is at the same time put down as the old or original
citronella grass of Ceylon, it is more probable that the statement
is due to some mistake. As to the Lenahaiu variety we haA^e
more precise information. It originated about 1885 near Matura,
in south Ccjdon, presumabty in a plantation, and in a short time
almost entii’ely replaced the old grass, on account of its being so
much hardier. Mells says of it : “It is in general appearance very
lilce the Mdnd grass found on g)aianas up country.”

(4) Cymhogjogon confertiflonis. — ^This grass is in all probability
the parent plant of the citronella grasses. In Ce 3 don it is one of

29-1

PE BP U 31 E B Y

the nio=;t conspicuous elements of the vegetation of the palanasz
Tn strong sunshine it emits an overpovering odour of citronclla.
Tlie Cingalese name for it is 31dm, vliilst it is called Bamtc in the
Nilgui vernacular.

{;>) Cymhopogon jlcxuosns. — Tliis grass, formerh* known as
Androp)ojon Jlcxvasm, Xces c.r Stcud., is known as Malabar or
Cocliin grass, and is distributed in the Tinnivelli District and in
Travancore, and during the past few years a large acreage has
been planted with the grass.

According to Stapf, Eheede, in his Hortus i\Ialabaricus,”
described a grass under the name Kodi-pidlu, and its illustration
is that of a grass very common tlu’oughout Travancore and the
adjoining district of Tinnivelli. Bottler knew it, and put it down,
though with some doubt, as Andropogon Nardns, which it resembles
very much indeed. Ainslie (1813) mentions it as Stihlcanaroo-
pilloo and “ gingergrass ” (the exact equivalent of the Tamil
name), and says of it : “ This is a variety of the grass which is
well known in Lower India by the name of the lemongrass ; it
differs, however, from it in this respect, that, on being chewed,
it has a strong flavour of ginger. It is very common on the
Com'taUam Hi l l s in the Tinnivelli District, where the natives
consider an infusion of it as stomachic and febrifuge.” And later
on (182G) he adds : “ The natives occasional!}’- prepare with it
an essential oil.” This, I believe, is the first record of oil being
prepared from Malabar grass. IClein collected the grass in 1818
on the same hiUs, and his specimens, which are also marked

Snchinari gBlhi, Tam. ; gingergrass, Ang. ; Androp)ogon Nar-
dus (?),” leave no doubt as to its identity vdth the plant from
which the Travancore or Cocliin lemongrass oil is produced.
Wight subsequently distidbuted specimens of the same grass as
“ Andropogon ficxnosus, N.E.” It was not, however, described
until 1855, when Steudel published a description, retaim’ng for
it Nces’ name ; but not much notice was taken of Stcudel’s
species, winch, if mentioned at all, was usually cited as a synonym
ol- Andropogon Nardus, as, for instance, by Bentley and Trimcn,
who, moreover, figured it as Andropogon Nardns. In 1889, Hackel
distinguished it as a variety of the tj’pical Andropogon Nardns
(citronclla grass), and the same jilace was given to it by Hooker
in the “ Flora of British India,” but neither author coimccted
it with the lemongrass oil of Travancore, which very generally
was treated simplj- as “ lemongrass oil.”

I\Iorphologically, C. flexnosus differs from the other species of

295

PBBFU MERY

t-lie Narchis series by its large, loose, greyish or slate-coloured
panicles, the branches of which are particularly slender, long,
flexuous, and often drooping, and by the less conspicuous spathes
and the smaller, usually very slender and acute, spikelets. The
basal leaf sheaths are rather narrower than those of G. Nardns
and C. confertifiorns, and are not reddish within.

When the Malabar grass oil — ^this name, 'svhich is used in
Barber’s collection, is preferable to the name Travancore lemon-
grass oil — ^v^as first exported cannot be decided precisely ; but the
“ lemongi’ass oil ” mentioned by Pereira (ISoO) as imported into
England from Cochin was very likely the oil of G. flexuosiis, and
not of G. citrakis. In 1859, Major Heber Drury, vviting to
D. Hanbimy and referring to a specimen of G. flexuosiis which he
had sent him, says : “ Erom this species (and from this only)
lemongrass oil is distilled in Travancore.” Eour years later
Hanbury received the same plant from E. G. Waring, vdth this
note : “ Andropogon (?), wliich yields the lemongrass of Travan-
core — abundant on the plains — is not cultivated.” The statement
in the “ Pharmacographia Indica,” vol. iii., 1893, p. 565, that
the oil is distilled in Travancore from Anjengo northwards, and
that the grass is burnt at the end of the ch’y weather, no doubt
also refers to G. flexuosiis, and not to G, divaius, as the authors
of that work believe. It is probably due to this confusion that
Gildemeister and Hoffmann saj’’, quoting Dymock, Warden, and
Hooper as their authorities, that “ the grass is ciiUivaied on a
large scale onlj^ on the Malabar coast in Travancore, on the
western slope of the mountains, north of Anjengo.” I\Ir. T. E.
Bonrdillon writes quite recently from Quilon that only Avithin the
last year or two extensive areas have been planted up with the
Malabar grass. As the Travancore grass oil is not commercially
distinguished from the oil of G. citraius, both being sold as
lemongrass off, it is difficult to decide as to which oil pubhshed
analyses refer. At all events, according to Stapf, the soluble East
Indian lemongrass off is derived from this grass.

(6) Gijmhopogon coloratiis. — ^This grass has a powerful lemon-
grass odour, and is found from the TinniveUi District to the
Anamallai Mountains, and also in the Madi’as Presidency. It
may be sometimes mixed with G. flexuosiis for distillation
purposes.

Practically nothing is known of the conditions under which
this grass grows ; but it has a distinctly xerophytic habit. It is
a highly aromatic grass. There is, however, no evidence that it is

296

P Eli F U M E BY

used for extracting oil or for any otlier purposes, xinlcss it is one
of the “ leniongi’asses *’ of the Slalabar district to wliich the
following extract from the Madras Mail refers : “ The natives of
Ernad and Waluvanad empirically distinguish no fewer than
twenty-seven species of lemongrass, but say that only five of
these varieties possess a commercial value. They also state that
the most valuable of these varieties does not blossom. Ernad
and Waluvanad, I am reliably informed, arc full of hills, on which
lemongi'ass grows vild and could be had virtually for the collect-
ing.” The variety which does not blossom is very jirobably
C. ciiralus.

(7) Cijmioj)ocf07i cilratiis . — Stapf is of opinion that this plant
is that from which the lesser soluble lemongrass oils are distilled.
Formerly known as Andropogon ciiraias, it is referred to by
Samuel Bro^vne in his “Seventh Book of East Indian Plants”
in the following terms : —

“ Tliis is a most delicate sort of fragrant Gt'ass which being
rubbed smells like Bainne and Lime or Limon peel together. The
Portuguese Wo^nen fume their children -with it, and give the
Decoction of it with other things for Fevers and to strengthen
weak stomachs ; but the Natives use it not, which together with
its gi’owing in Gardens on the Sea coast and not up the Countiy,
as I can yet observe, makes me think the Portuguese brought
this from other parts and planted it here ; certainly, so exceUeut
a Plant of such Fragrant and Aromatik taste must have many
Vert lies. I use it in many cases, and generally with success. While
I was VTiting this, in came a Person, who saj’s, that about 30 3 ’-ears
ago, viz., about 1G6G, one Antonio Palia, brought 3 Pots of tliis
Grass from Batavia to Paliacut, one of which he sent to a Garden,
here at Madrass.”

The Portuguese in India termed it Herha cJieirosa, the equivalent
of the Tamil Vasana-pnllu, and the Dutch named it Sereh, a name
b.v which the grass is stiU ImovTi in Java.

It is probable that the grass was inti’oduced into Cejdon during
the Dutch occupation of the island.

The comiiarativeh’- recent date of the cultivation of the lemon-
gi'ass in India is evident from the nature of the established
vernaculars. The Tamil Vasana-g^illu is merelj’’ the equivalent
of the Portuguese Herha cJieirosa, under which name it was
probablj” introduced. The term was taken up unchanged, or
almost so, in Walavalim, Canarese, and Telegu. Another Tamil
name, Karpfa-a-pulhi (camphor grass), is equall}' descriptive, and

297

PERFU MERY

the same applies to the Gujerati and Marathi vernaculars, ■which
mean “ green tea,” whilst the Dukni name given by AinsHej
namely, Naring Ice has lea glians^ is a direct translation of “ lemon-
grass.”

The plant was sufficiently attractive in India to cause its early
introduction into the colonies of, those European powers which
had possessions in India. It was introduced into Jamaica at the
end of the eighteenth centmy, and later into the Spanish and
French colonies, and, probably through the Portuguese, into East
Africa. In the Malay districts it is universally grown as a medicinal
and kitchen herb. Its history there goes back, no doubt, far
beyond the arrival of the first European invaders. We hear of
it almost simultaneously from the Pliihppines and from Java as
early as the first half of the seventeenth century. In 1635, Juan ~
Eusebius Nieremberg, a Spanish J esuit in the Philippines, describes
it quite unmistakably under the name of Tanglat a term still
in use for “ lemongrass ” in the Tagalog and Visayan dialects
(spelt Tanglad). The passage, which is worth quoting, reads :

“ Tanglat. It is a herb springing from a bulbous root, the swollen
base of the leaf tufts, whitish-red vfithout, yellowish Tidthin ;
from it rise 10-12 leaves, about 1 m. long, rather rough and
moderately green ; there is, however, neither a (flowermg) stem
nor fruit. The whole plant has a scent lilce that of lemon flowers,
but stronger. Cooked, it improves the taste of stale boiled fish ;
put into wine it gives a pleasant flavour, and it imparts a delicious
odour to sauces and spices. The hquor distilled from it is almost
scentless until exposed to the sun ; but this being done, it usually
exhales a pleasant odour, and appfied to the face seems to sharpen
and invigorate all senses and the head.”

Stapf summarises the uncertainty of the origin of the grass as
follows : —

“ As the lemongrass is only known in the cultivated state, the
question arises, what is its origin ? I am afraid it is yet too soon
to give a satisfactory answer. It is true there is not, among the
Malayan species of Cymhopogon, so far as I know them from the
collections at Kew and the British Museum, a single one which
suggests itself to my mind as the spontaneous state of the lemon-
grass, and Bumphius’ statement that it occurs in the "wild state
in Amboina is open to doubt ; but our knowledge of the Gymho-
pogons of the Malayan region is still so imperfect that the possibility
of the lemongrass having originated there is by no means excluded.

“ The Oyrnhopogon most closely approaching C. citrakes that I

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PE RFU B I'

linvc i? Cymhopogon pcnchiJus, Stapf {A-ndropoyon j^'-inhdus,
Xi (.)■ Stciul.). collected by Wallicli in Xe2:)al. by Hooker. Kurz.
and Clarke in the Sikkim Tcrai, and by C-iriiiith (No. G7G3) in
‘ Bcngala.' Xo vernacular name i? given, there is no information
concerning its j^roperties and uses, nor has it ever been connected
with the lemongrass, and to do this, in the light of our present
Icnowlcdge of the history of the latter, would involve a hypothesis
bolder than I dare to advance. Another allied form, presumably
from the same region, but less like lemongrass, and distinguished
therefrom by less hairy racemes, borne on long common peduncles,
which are frequently exserted from the sui^porting sheath, and b3'-
smaller as relatively much broader sj^ikelets, was figured as
‘ Avdropogon ScJKxnrtntJnis ' (qua ‘ lemongrass ’) by "Wallich. and
referred to Andropogon Nardus, var. cxscrtiis, b3'’ Hooker. It was
in cultivation in the Calcutta Botanic Garden, and maj’^ have
been raised from the seeds of a fairly distinct Androqwgon of the
Nardus series, wliicli extends from the Saharanpur Terai to the
Garo Hills, and possesses ver3’' aromatic citron-scented leaves.
However this may be, neither Wallich’s plant nor its presumably
wild representative agrees sufRcientl3’ with the lemongi-ass to
suggest the derivation of the latter from either of these species.”

(8) Cymhopogon Martini . — This grass is the plant from which
palmarosa and gingergrass oils are obtained. The differences
between the two oils are so pronounced that some marked
difference between the distillation materials must e.xist. It has
been suggested that the period of growth at which the grass is
cut is responsible for the difference in the oils. But this is highl3’-
imiorobablc, and it seems certain that there are two varieties of
the gi-ass, whoso morphological differences are not 3'et settled.
The following account of the foundation of the .species is given
b3' Stapf, the grass having been originalh' named Androjiogon
Martini. It is known in India to-da3’- as Rusa or Rosha grass : —

During the Avar of 1790-1792 against Tipu Sultan, Claude
Jlartin, aa'Iio joined the expedition in 1791 as a Commissioner of
provisions and aide-de-camp to Lord CoriiAvallis, collected “ in the
highlands of Ballaghat ” the seeds of a grass Avhich had struck
him, owing to its excellence, as a fodder plant, as avcII as on
account of its pungent taste and aromatic odour, aaIucIi Avas so
strong as to impart itself to the milk of the coavs which fed on it.
From the seeds he raised an abundant crop at LucknoAv. He al.^o
supplied Roxburgh “ AA'itli a small stalk, roots and seed.” The
“ small stalk ” is not preserved ; but Roxburgh grcAv the grncs

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PERFU MEET

from tlie seed iii the Calcutta Botanic Garden, and of the specimens
thus raised there are two at the British Museum, one from Eox-
hurgh’s herbarium, the other from General Hardmcke’s collection.
The first is named “ Andropogon Martini ” in Roxburgh’s own
hand ; the other, under the same name, bears the date Feb-
ruary 18th, 1789. The name did not appear in print until 1814,
whilst the description, although efficiently written before 1799,
was only published in 1820.

Dr. Maxwell, Assistant Surgeon at Asirgarh Fort, in Nimar,
wrote, in 1824, a letter to the Medical Board of the East India
Company, in which he called attention to a fi-agrant grass which
was “ found in great abundance On the sides of the liill fort, as
well as all over Malwah. From it,” he says, “is extracted a
highly pungent essential oil (when in its pure state), which I can
from experience confidently recommend as of the highest benefit,
when applied by friction, in rheumatic affections,” and, further,
that “ it is prepared by a very rude process under Jaum Ghaut,
hi the vicinity of the station of Mundlaish’.” ■ The specimens
which he sent with his letter were submitted to Wallich, who, in
his reply to the Medical Board, reported as stated above, adding
that he himself had found the plant abundant in Nepal. In the
following year, J. Forsjfili, who had been directed to investigate
the matter on the spot, presented a paper to the Medical and
Physical Society of Calcutta, in which he gives a detailed account
of the preparation and the sale of the oil and the conditions under
which the grass grew and was gathered. He also gives Roosa-lca-
Tel as the native name of the oil. Of the grass, he reports that
it “ is met vfith in frequent distinct patches in the jungle tlu’ough-
out the province of Nemaur, but in greatest abundance along the
foot of the Vindliya Range, near Nalcha, at wdiich two places
only, I believe, it is prepared, at least' to any amount. About
the latter end of August it begins to bud, and continues to flower
in tolerable vigour till the end of October, d-uring which period
alone it gives out the oil in’sufficient quantity to cover the expense
and trouble of its preparation, as after this it speedily dries up,
and what httle oil it does yield is extremely acrid, and unfit for
use. . . . The oil is obtained from the grass by distillation . . '.
the plant is cut across where it begins to give o.ut its flower, and
bound up into small bundles. . . .” A few years later (in 1830),
Charles Hatchett, F.R.S., a prominent chemist, received a sample
of oil from a Mr. Samuel S'winton, who had been in the East India
Company’s service for many years and had resided for some time

300

PEliF U 21 E R Y

in Mnlwa. Hatched made the grass ■ndiich ^dclclcd this oil the
subject of a somewhat confused paper, entitled “ Spikenard of
the Ancients ” (183G). Swinton, like iMaxwcll, first became
aerpTainted with the oil (wliich lie says is called JRhoJiscc-kc-Tell
by the natives) as an effective remedy in severe attacks of
rheumatism. He also stated “ that althoxigh the jfiants are found
in other parts of India as well as in Malvah, j^et those which
grow about the Jaum Ghaut arc preferred, and gathered in the
month of October, when the seeds forming the ears or spUces have
become fully ripe. At that season, however, in the places where
this gigantic grass is x^roduced, the jungle fever is so prevalent
that the peasantry who collect it will not ex^Dose their health . . .
unless tempted b}’’ very high remuneration. . . Hatchett
further adds : “ Mr. Swinton was informed by them (the prmcipal
natives) that it has been prepared in and about Malvah from
time immemorial, at first probably by the Parsees, although at
present it is entirety in the hands of the Borahs, a very com-
mercial people, forming a sect of jNIoslems, whose cliief resides at
Siu’at. The oil is obtained fi’om the spikes, which, when ripe,
are cut until a portion of the stem about 1 foot in length, and
are then subjected to distillation. Only a small comparative
quantity of the oil is consumed by the natives, the greater part
being now, as was the case in very remote times (according to
tradition), sent as an article of commerce to Arabia.” Finally,
it is stated that “ the odour of the plant is so powerful that,
although camels unll cat almost any vegetable, yet they will not
browse on this. . . Neither the production nor the export of
the oil can, however, have reached any considerable dimensions,
as jacquemont, who, in the spring of 1832, visited Nalcha and
Jaum, and gave a very full account of Slalwa, does not mention
the grass or the oil. The grass, it is true, might have escaped
him, as at that season it must have all been dried up.

How far there is any truth in the tradition that oil has been
distilled from the Rusd grass “ from time immemorial ” we do not
know. The authors of the “ Pharmacographia Indica ” (vol. iii.,
p. 558) merely suggest that “ the industry commenced in the
eighteenth centurj*, wlulst Kliandeish was in a flourishing con-
dition unders its Mahometan rulers.” However this ma}’- Ijc,
there is sufficient evidence that the grass must have been known
to the Aryan j)Coplcs of India for a very long time. Rohishcr,
the Sanskrit equivalent of the Hindi Ritsd, occurs in “Susruta ”
and in some of the earliest Sanskrit dictionaries. Another name

301

PERFUMER Y

in Sanskrit, evidently from the same root, is' Rdseni. Variants
of these terms are generally recognised vernacular names in the
Hindi, Gujerati, and Mahrati dialects. Curiously enough, the
name does not appear in the earher Persian pharmacopoeias, the
first record of it, Rus, being apparently in the “ Makhzan-el-
Adwiyaii ” (1771). According to the authors of the “ Pharmaco-
graphia ” (vol. iii., p. 557), C. Martini is also “ the Bhustrina or
Blmtrina (‘ earth grass ’) of the Raja Highanta,” and among the
synonyms which it hears we may mention Gandha-Kheda and
Gandha-trina (“ odorous grass ”), 8u-rasa (“ well-flavoured ”), and
Su-gandlia {“ having an agreeable odour ”).

(9) Cymbopogon ccesius. — ^This grass, formerly known as Andro-
pogon ccesius, or Kamakshi grass in Tanul, very closely resembles
the -Rusd gi’ass or geranium grass used for distilling palmarosa
oil. In the Carnatic the Rusd grass is replaced by a closely alhed
form vdth more slender and more branched culms, usually from
|- to 1 metre high, vith narrower, thioner, often almost flaccid
and very glaucous leaves, and vith generally smaller panicles,
which seem to retain their glaucous colour, or merely turn straw
colour when mature. The structure of the spikelets is, however,
that of G. Martini, and so closely does the Carnatic grass in some
instances approach the narrow-leafed state of’ G. Martini that
there would be no difficulty in constructing a chain of intermediate
stages, linldng together both forms as completely as possible.
Those transition forms are, however, so far as I can see, confined
to the border districts where the two grasses meet ; elsewhere
they are sufficiently distinct.

The oldest specimens of the Carnatic grass on record are a
specimen in the Plul^enet herbarium at the British Museum, and
several in the Du Bois herbarium at Oxford, aU of them collected
near Madras at the end of the seventeenth or in the early years
of the eighteenth century ; but it is very probable that a passage
in a letter by Herbert de Jager to Rumphius, dated July 6th,
1683, also refers to it. Contesting the view of Bontius and others
that the Sereh of the Malays is identical with the Scho&nantUim
of the herbalists, and, in support of his argument, he says : “ I
have become famfliar with the true and genuine SchcenantJmm
in Persia, and particularly on the coast of Coromandel, where I
have traversed whole fields of that grass, which is about 2|- to
3 feet high, and the scent of which may be noticed from afar,
particularly during the night, 'when dew falls, or in day-time
when it rains, whilst in sunsliine and fine weather not much

302

PER F U M E R Y

O'lnnr i< perceptible. In Golconcla this Scho:nanOium ground into
pcnvder is u.^ccl for washing the hands on account of the sweet
scent it imparts to the water ; though the odour docs not persist
vchen the Iiands get diy."’ Neglecting for the present the question
as to wliat the SclKxnantlmin powder of Golconda was, there
can be little doubt tliat the fragrant Coromandel grass, of wliich
there veere whole fields to traverse, was the Kdmdtci-])ilhi of the
Tamils. Of this name wo hear for the first time in Samuel
Browne's “ Seventh Book of East Indian Plants,” edited and
commented on by Petiver (1702). The plants which form the
subject of the paper were collected “ between the 15th and 20th
June, A.D. 1G96, in the ways between Fort St. George and
Tripjjetcc, wliich is about 70 miles oS.” One of them was
ComacJiee inllee, and of it Browne saj’^s : “ This is Schoenanth,
which the natives here have not in great Esteem,; sometimes in
the i\Ioors’ Camps, the Horses, Camels, and Oxen which cany
biurthens eat nothing else ; it is generally 2 or 3 feet high here
about (but near Color in reech sojd, I have seen it 8 feet high)
[tliis gigantic grass is no doubt C. Mariini] and thick as a Quill
or small Reed ; It’s sometimes by the natives put into their
Decoctions for Fevers, and ivitli us is deservedl3>' of more esteem.”
Petiver identified the Comach-ee pillea with Plukenet’s Gramm
Daciylon Maderas]jaie.me, figured on Plate 119, Pig, 2 of his
“ Almagesta ” (1691), the type of which is in Plukenet’s herbarium
— ^it is the specimen referred to above.

C. ccEsius seems to inliabit the greater part of the Carnatic,
from the extreme south to the Chingalpat District. It is evidently
common,- on the whole, in that region, but little use seems to have
been made of it so far, except as an occasional domestic remed3^
There is, however, among the specimens communicated bj’- JB.
Barber, one with a note to the effect that it is the “ grass from
which Jlr. Proudlock has been distilling oil.” A short account
referrmg to it is contained in the “ Administration Report of the
Government Botanic Gardens and Parks, the Nilgiris,” for 1901,
p. 0. According to this report, the grass was obtained from Arni,
in the North Arcot District, where it is stated to grow in great
abimdanco. The yield of oil from a freshly cut sample received
at the end of December w'as 0-431 per cent. Another and larger
quantity, wliich was received in April in a thoroughlj^ dri’- con-
dition, jnelded 0-711 per cent, of oil, the differences in the jdcld
being attributed to the first lot being fresh, whilst the other was
dry.

303

PEBFUMWB T

(10) Gynihopogon polyneuros. — Just ^as C. Martini is replaced
in the south-east of the Deccan Peninsula by G. coesius, so
another species takes its place in the south-west. This species,
G. jiolyn&uros, is, however, much better defined than G. ccBsius,
It is a moderately robust grass with a tendency to copious branch-
ing from the collar so as to form dense tufts of culms, with
somewhat persistent narrow basal sheaths, rather fat, smooth
blades with a rounded base, more or less glaucous beneath, and
often suffused with pm’ple along the margin, and with short,
contracted variegated panicles, the herbaceous sheaths being
usually deep brown-green with a narrow scarious • margin, the
spikelets being green in the lower part, and more or less blackish-
purple in the upper. It was first distributed by Wight (No. 1705)
under the name A-ndropogon versicolor, N.B., a name chosen, no
doubt, in allusion to the variegation of the inflorescence. Nees
never pubhshed a description of it. On the other hand, Steudel
has, in his “ Synopsis Plantarum Graminearum ” (1855), p. 388,
an “ Andropogon versicolor , Nees MSS.,” under which he c|uotes
“ A. Schoenanihus , Wall. Cat. n. 8794L.” Wallich’s Cat. n.
8794L.” is in Wallich’s ovm herbarium identical with n. 8794K.,
which Steudel [loc. cit.) cites under Andropogon clandestinus, Nees.
Steudel’s description of Andropogon versicolor agrees neither vnth
Wight’s No. 1705, issued as ” Andropogon versicolor, N.E.,” nor
vdth Wallich’s n. 8794L. It is mot clear what the plant which
Steudel had in mind was ; it cannot well have been Wight’s
Andropogon versicolor, N.E.’- Wight does not indicate the
locality where his No. 1705 was collected beyond the general note
“ Peninsula Ind. Orientahs.” It agrees absolutely, however, with
a grass which ha's freq^uently been collected in the Nilgiris, among
others by Hohenacker, who distributed it as 933, Andropogon
{Gymbopogon) nardoides )3 minor N. ah E.” ; this was made by-
Steudel the type of his Andropogon polyneuros. That name being
perfectly unambiguous, its specific component wiU have to be
i-etained for the NUgiri grass hi question in preference to versicolor,
although the latter has very generally been applied to it. Outside
the Nilgiris, G. polyneuros has so far only been observed in
Ceylon, where it is, particularly at higher elevations (up to 1,500
metres), a locally common plant. Thwaites has already called
attention to the ” rather agreeable aromatic odour of the
inflorescences of this species, adding that . the essential oil
appears to be situated principally at the base. of the spikelets.
According to a note in the Tropical Agriculturist for 1901

304 =

PERFUMERY

(p. 873), the odour of the crushed leaves resembles that of fennel
or anise.

(11) Vcimria zizanioidcs is the cus-exts or Uim-hlias grass, from
'vvluch vetivert oil is produced. It 'was former]}^ knov-ii as Amlro-
pogon mvrkatus. In the vdld state it is distributod over most of
British India and Ceylon, being found on the banks of rivers and
on rich marsliy soil up to an elevation of l.SOO feet. It is some-
times cultivated, as, for example, in Rajputana and Chutia-
Nagpur. It is cultivated in the I^Ialay districts, the West Indies,
Brazil, and Reunion.

The Hindu name for the grass is J:Jias-kJias^ the name vetivert
being of Tamil origin. Jones in 1795 identified the Ueiva of
Kalidasa with and Hessler did the same in his transla-

tion of the Ajmrvedas.”

The natural area of this grass in India and Ceylon includes
practicaU 3 ^ the whole countrj^ in the north up to altitudes of
GOO metres. Although common in many' parts of the country,
particularly on the banlis of rivers and in rich marshy soil, it is
also at present, as in Rheede’s time, occasionally cultivated, as,
for instance, in Rajputana and in Chutia-Nagpur, Eastwards the
area extends into Burma, Tluoughout the Llalayan region, how-
ever, it ocem’s only in the cultivated state or as an escape from
gardens. It has also been introduced into the Mascarenes, the
West Indies, and Brazil ; but it seems that in these countries oil
is not distilled to any’' appreciable extent, except perhaps in
Reunion, where the gi’ass must have been in cultivation for at
least 100 years, -as the first sample of vetivert oil that was
chemically’' examined (in 1809) came from there. (See also under

Vetivert Oil/')

(12) Andropogon odorahis. — ^Tliis grass, knoum in India as
XJsadhana^ is a little-known grass which was discovered by^
Dymiock at Thana in 1875, and mentioned on account of its
strong odour of ginger under its vernacular name, Usadliana, in
the first edition of his “ Materia Medica of Western India ” (p. G93).
In the second edition of that work (p. 853) it was referred to
Andropogon Mardiis. Subsequently it was, however, recognised
as a new species by- Sirs. J. C. Lisboa, and described as A. odoraliis.
This very aromatic grass is used by the peasantry of the Tliana
District for medicinal purposes. An essential oil of a golden-yellow
to a deep sherry^ colour, vith a distinctive odour, was obtained
from it by^ distillation, but it lias not y^et become an article of
commerce. The odour is, according to the “ Pharmacograi)hia

305

PBRFU MER Y

Indica,” vol. iii., p. 570, at first that of cassia and rosemary, but
afterwards that of oil of cassia or, according to Gildemeister and
Hoffmann, that of pine-needle oil.

GRIFFES DE GIROFLE. — ^The flower stalks of the cloves,
separated whilst they are dr^dng, are knovm in Zanzibar as
Vihunia, and in France as Griffes de Girojle.

GUAIACUM WOOD OIL. — See “ Bulncsia Sarmienti, Oil
of,” and “ Champacol.”

GUAIOL. — ^Although this body has not any odour value,
it is of interest as being the only well-identified constituent of the
so-called guaiacum wood oil — ^the oil of Bulncsia sarniie 7 iti. It is
a sesquiterpene alcohol, of the formula CigHocO, melting at 91°,

20 °

of specific gravity 0*9714 at — , and having a refractive index

1*5100 at 20°, and specific rotation about — 27°. (See also
Gandurin, Berichic, 41, 4359).

GUM THUS.— See “ Boswellia Resin.”

GURJUN BALSAM OIL. — Gurjun balsam is an oleoresin
derived from various species of Dqoterocarpu^. It is a viscous
substancccloscl}' resembling balsam of copaiba in general charac-
ters, and is used to some extent as an adulterant of copaiba.
It has no direct relationship with legitimate perfumery, but is
found as an adulterant of manj’- essential oils. The oleoresin, on
distillation, yields about 50 to 60 per cent, of an essential oil,
having a specific gravity 0*915 to 0*935 ; optical rotation, — 30°
to — 135° ; refractive index, about 1*5050 ; acid value, 0 to 1 ;
and ester value, 4 to 8.

Gurjun oil is a colourless liquid of sharp odour, but of no value
as a perfume material. It is, however, of interest on account of
the fact that it has been used to a considerable extent as an
adulterant of Indian palmarosa oil. It is easity detected by
analysis in this oil ; and as palmarosa oil is used as a raw material
for the production of geraniol, traces of the adulterating gurjun
oil remain in the geraniol produced from the palmarosa oil.
Geraniol so produced is used to some extent as an adulterant of
otto of rose, and if the adulterating geraniol has, in fact, been
manufactured from palmarosa oil already adulterated with
gurjun balsam oil, traces of the adulterant are easy to detect in
the otto of rose. Gurjun oil, or any oil containing more than traces
of it, gives the following characterisic colour reaction, wliich is a
practically definite proof of the presence of the oil as an adul-

306

PERFU 2IEBr

tcrani. If 5 to 10 drops of the suspected oil- are added to a
luixlure of 10 c.c. of glacial acetic acid containing about 5 drops
of nitric acid, a violet colouration -vrill result almost immediatel 5 ^
If no colour results vithin one minute, it maj" be taken for granted
that this adulterant is absent. This oil has no interest to per-
fumers other than as an adulterant, as above indicated.

HARDWIGKIA BALSAM. — ^The so-called African copaiba
is of no interest to the perfumer, e.vcept that the essential oil
distilled from it is from time to time used as an adulterant of
perfumery oils. There is considerable doubt as to the botanical
origin of the balsam. It is usuall}- ascribed to Ilardiuiclda Mannii.
It has also been said to be the product of Oxystigma Mannii, and
it has recently been suggested that it is derived from Daniclla
iliurijcra. It is a thick, viscid oleoresin, containing about 40 to
53 per cent, of essential oil. The characters of the balsam are as
follows : specific gravity, 0'985 to 0-998 ; acid value, 53 to G5 ;
ester value, G to 10. It is also known as iUnrin balsam. The
essential oil is a colourless liquid having the following characters : —

Specific gravity . . . 0-915-0-932

Optical rotation . . . -{- 5° to -f- 37°

Refractive index . . . '1-5000-1-50CO

Acid value .... 5-10

Ester value .... 0-G

Ester value after acetjdation . Up to 12

It does not yield any characteristic colour reactions b 3 ' which
it can bo detected, as does the similar gurjun balsam oil, so that
the best method for its detection lies in a careful comparison of
the ph^'sical characters of the various fractions of a genuine and
a su-si^octed oil. A pure African copaiba oil, distilled bj- the
writer (E. J. P.) and C. T. Bennett, jiclded the following four
equal fractions of 25 per cent, each, on distillation : —

Specific gravity.

Rotation.

Refractive index.

1 1

-f 17° 30'

-f28°30'

3 1

-b 4G°

4 !

• -{-55°

Similar results were found with other normal samples of
African copaiba oil. Oil of peppermint has been found by the

307 CO-2

P E PEI' :!/ E P y

writer grossly adulterated with this oil. The influence of the
adulterant is cleai-ly indicated in the fractionation of the oil, by
the entirely abnormal increase in s])ccifio gravity, oj)tical rotation
to the right, and j-efraetive index (jf the laler fractions of the
adultera(od][oil.

HAWTHORN PERFUME.-'.rhe basic material used for
the manufacture of fdl hawthorn ])crfumes is arliticial hawthorn,
usually known as aubejjine {ride "Anisic Aldehyde’’), ^^‘lrious
lloi-al extracts are based u])on this to round it off and give it a
distinctive odour, according to the individual })crfumer's taste.
The natural ])crfume of mayblossom, Crdlrrgur o.ri/rdiithn, is not a
commercial article.

HEDYOSMUM.— The so-called tobacco bu.sh of Jamaica is
llrdi/osminn uuUnis. .Tt yields an essential oil which recalls the
odour of certain tobaccos, .and is said to be of value as a soap
perfume. It has so far. however, not i!])])cai-(-d on the marked as
a commercial article.

HELICHRVSUM OILS.— Various species of heliehry,-um,
a genus belonging to the natural order Co)i>posila\ yield essential
oils having an odour value, lldichru.snm f-'dralilc. according to
1‘Tanccsconi and Sernagiotto {Gazz. Chin}. -14, 1!114, ii., 410).
yields an oil with an odour recalling that of roses, and having a
s])ccilic gravity 0-tK)2 ; o]itieal rotation. — ll-?” ; and refractive
index, 1-47G0. Its constituents are unknown.

lldichrijsnm arcnariinn yields 0-4 per cent, of essential oil of
powerful aromatic odour recalling that of celery. Its specific
gravity is 0-021 at 20° ; acid value. M-.a ; and ester value, 0. It
probably contains paro-cresol. Jlclit'hri/.sum angn-'^tifolium is a
fragrant herb widely distributed in southern Europe. It grows
in masses near (tenoa, and also in Hungary and Dalmatia.
Echinimcl Co. {Pc.porL October, 1002. 72 : A])ril, 1000. .77 ;
Api'il, 1014, 0.7) obtained from it 0-07;7 jier cent, of essential
oil of specific gravity 0-802 to 0-020 ; optical rotation, + -1° 25'
to — 0° 40'; refractive index, 1-4745 to 1-4S40 ; acid number
up to 15 ; and ester value, 20 to 124. The oil is rich in nerol,
partly in the free state and partly in the form of esters.

HELIOTROPIN. — The perfume of heliotrope, commonly
known as " cherry pie,” Avas for many years a great favourite,
although it has probably lost its popularity owing to its having
been overdone by aii indiscreet use of the artificial hcliotropin to
excess, with the result that inany perfumes containing it arc so

30S

PERFV ME li 1'

ptrong as to be vulgar and objectionable. Tlie orcbnar}- heliotrope
plant is a native of Peru, lldiolropiim. Pcnivianuin, belonging to
the natural order Boraginaccce. This plant vas introduced into
Europe about the middle of the eighteenth century. There are
a very large number of .“jpecies of the genus, which are for the
most part highly odorous, and which arc found distributed all
over the world, especially in tropical and sub-tropical regions.
The flowers are treated to a small extent for the natural perfume,
and the triple extract, absolute and concrete, are obtainable on
the market. The bulk of the hehotrope perfumes sold to the
public, however, are cither entirely or chiefly based on the
artificial heliotropin. This body very faithfull}' reproduces the
odour of the jdant, but is rather too crude, and requires “ rounding
off.” This is best acHeved by the use of a verj' small amount of
vanillin, together with a very minute quantity of benzaldehyde.
Numerous other bodies blend well vdth hcliotropin, but where
used to anj^ extent, result, of course, in a fanc}'’ perfume in which,
pro tanlo, the heliotropin has lost its characteristic dominating
odour.

It was in 1876 that Tiemann and Haarmann, m the course of
their researches on the perfume of this plant, recognised that it
was in the main due to two bodies, heliotropin and vanillin.
Various types of vanilla beans, and also the flower of the meadow-
sweet {Spircca Uhnaria), were also found to contain very small
quantities of heliotropin. In 1910 Elze found it to be present in
the essential oil of Pohinia psemlacacia, and soon afterwards
Dieterich claimed to have detected traces of it m ordinary’- bees-
wax. Its occurrence in nature, however, is rare, and wherever
it is found it exists in very small quantity, usually in minute traces.
It is probably formed in the plant by the decomposition of a
glucoside.

To-day the world’s supply of hcliotropin is derived from oil of
camphor, which contains a large quantity of safrol, the raw
material which jdelds heliotropin. Originalty, however, artificial
hcliotropin was made from the alkaloid piperine C'l^HjyNOa.
Pejiper (preferably Singapore pepper), which contains from 7 to
9 per cent, of the alkaloid piperine, is ground to a fine powder and
mixed with twice its weight of slaked lime and a little water, and
the mixture evaporated to drTOCSS. The dry mass is then
extracted \nth ether, which dissolves the alkaloid, which is left
behind on the evaporation of the solvent. The piperine is then
boiled for some time with alcoholic potash,' In* which means it

300

PERFUMERY

is converted into potassinm piperate’. Tins body is dissolved in
fifty times its weight of water, and is then oxidised by means of
potassium permanganate. The manganese oxide formed is filtered
ofi and the filtrate evaporated, when the heliotropin crystallises
out.

Safrol {q.v.) is the odorous constituent of oil of sassafras, but it
also exists to a considerable extent in camphor oil, from wliich it
can be obtained considerably cheaper than it can from sassafras
oil. In 1890 Eyckmann found that safrol yielded heliotropin, or
piperonal as it was then frequently termed, on oxidation. It was
also found that the yield was better if isosafrol were used.
Ciamician and Silber {Berichte, 1890, 23, 1160) found that, if
potassium permanganate were used for oxidation, a ketonic
derivative was formed which diminished the yield of heliotropin,
but that, if biclnomate of potash were used, this did not
occur.

In the commercial production of heliotropin camphor oil is
fractionally distilled on a very large scale, and the safrol so
obtained is heated with alcoholic potash, and is thus isomerised to
isosafrol in the same way as eugenol is isomerised to isoeugenol
for vanillin manufacture. The isosafrol is rectified, and is then'
oxidised as follows : A mixtm’e of 25 parts of bichromate of
potash, 80 parts of water, and 6 parts of sulphuric acid is poured
slowly into 5 parts of isosafrol with continual stirring, the tempera-
tm’e not being allowed to rise materiallj^-. When the reaction is
complete, the reaction mass is steam distilled and the distillate
is extracted with ether. On evaporation of the ether, the helio-
tropin, in an impure condition, is left behind, and is pm’ified by
conversion into its sodium bisulphite compound in the usual'
manner.

Several patents have been taken out for the manufacture of
heliotropin by oxidation of isosafrol by means of ozone (e.gr., British
Patent No. 6593 of 1895). There the oxidising agent is ozonised
oxygen, which oxidises the isosafrol, preferably dissolved in acetic
acid. When the oxidation is complete, the acetic acid is evaporated
in vacuo and the heliotropin extracted with ether and purified
by means of its bisulphite compound in the usual manner.
Heliotropin can also be made by treating protocatechuic aldehyde
with methylene iodide in the presence of an alkali. This method,
however, is not a commercial one, but has confirmed the constitu-
tion of the compound.

•Heliotropin is a white crystalline compound melting at 37°,

310

PEEEV M E i? r

Its perfume is po'u-erful and very sweet. It is, Iiowercr, injuriously
affected by. exposure to a temperature several degrees below its
melting jmint, and it shoiild therefore be stored in a cool place.
It is also better to keep it in a dark place, as the effect of strong
light appears to be adverse to the keeping properties of heliotropin.
Some perfumers always keep heliotropin dissolved in alcohol,
ready for use as required, when decomposition is largel 3 ^ obviated.
There arc many fanc}' names resemblhig hehotropin, but most
of them mereh- disguise a mixtm'e of pure heliotropin with a little
vanillin or coumarhi, and a fanej* price is paid for them. The
intelligent perfumer will purchase pure heliotropm and do his o%vn
blending. The determination of the melting point is the best
criterion of the purity of this substance. This should be sharp
at 37° to 38°, a gradual melting indicatmg adulteration. If an
exhaustive examination is required, hehotropin may bo converted,
bj’- excess of bromine in carbon bisulphide, into bromopiperonal
CcHoBr.(CH 0 )( 02 .CIIo), winch forms ciystalline needles melting
at 129°. It also forms two isomeric oximes, of which one melts
at 110 ° to 112 °, and the other at 146°. It jdelds a semicarbazone
melting at 146°, and a nitro-derivative melting at 94° to 95°.

HELIOTROPYL-ACETONE.— This body, or piperonsd-
acetone, is a crystalline compound melting at 55°, and boiling at
165° at 12 mm. jmessure. It has a characteristic and yerj’- pleasant
floral odour. According to Kaufmann and Radoscvic {BcricJdc,
1916, 59, 675) it can be prepared by emulsif^dng an acetone
solution of heliotropin with water and treating the emulsion with a
40 jocr cent, solution of caustic soda. This results in the formation
of pipcronal-acctone melting at 107° to 108°. Hj'drogen in the
presence of colloidal palladium reduces this to pipcronjd-acetone.

HEMEROGALLIS FLAVA. — ^This plant is knovm as the
j'cUow tubero.se. Its natural perfume is not obtainable, but an
artificial perfume is sometimes made bj’- using terpineol, hych’oxj'-
citroneUal, am 3 d sahc 3 date, and similar synthetics. It is not, of
cornse, more than a rough cop 3 ’' of the natural perfume.

HEPTANE. — ^This bod 3 * is one of the alij)hatic or fatty h 3 'dro-
carbons which arc of rare occurrence in essential oils. It is a
vcr 3 - volatile liquid of the formula C 7 II 15 , of specific gravity 0 - 688 ,
and boiling point 98° to 99°. It has been foimd in the essential oils
of Pinits Sal{nia7ia, Pintis Jeffreyi, and a few other allied species.

HEPTINE CARBONATES.— HeptineCH,(CH2)..C i CH is

, 311

PERFUMERY

the parent substance of a new and most important series of
artificial perfume materials. Of these amyl-heptine carbonate has
ah’cady been described. It mil here be convenient to deal with
tlie heptine carbonates together with allied acetylenic esters.
The chemistry of this important group of bodies is w^ell sum-
marised b}’’ Valli-Donan {American Perfumer, 1923, 133, and Rev.
de la Parfximerie, March, 1923, p. 4). He points out that among
the constantly increasing number of organic synthetic products
wiiicli have been found useful in perfumeiy, methyl heptine
carbonate deserves a special place, on account of the unusual
interest of its method of manufacture, as Avell as the remarkable
advantages of its use.

The preparation of this ester requires the most painstaking
technique and delicate management at the disposal of modern
chemistiy. Nevertheless, its development from the laboratoiy
to the factoiy scale has been effected -without mishap, the industrial
product attaining, from the start, a high degree of perfection.

It was in the course of the research of kloureu and Delange
{Bull. Soc. Gliim., 1903, 29, 648) that method heptine carbonate
was discovered, together with numerous other derivatives ha-\dng
the triple bond.

Metlyd heptine carbonate

CH 3 .(CH 2 ) 4 .C : C.CO 0 CH 3

is a colourless hquid, mobile, boihng at 107° at 20 mm. pressure,
and having a specific gravity 0-9524. When pure, it has a strong,
sharp, penetrating, disagreeable odour. But wdien sufficiently
diluted, it gives off a very fine and very persistent fragrance of
fresh violets, which renders it very valuable m the compoundhig
of extracts and original perfume compositions.

In conjunction with the ionones and metlyl ionones, it is
capable, in some measure, of replacing violet extracts, and of
imparting an original note to the perfume bases, more and more
complex, used by the perfumer.

If one considers a true acetylenic hydi’ocarbon of the general
formula

R.C : CH,

it is clear that the end hydrogen atom, the one which is attached
to the carbon atom bearing the triple bond, possesses acid
properties, and that it is therefore possible to replace it b 3 ^ a
monovalent metal, for example, sodium :

R.C i CNa.

312

PERFUMER T

The Forlium h>tlrocarbon corai^ound thus formed is a molecule
capable of many reactions, and, in particular, reacting especially
easily v/itli halogen derivatives.

If it is treated vith a chlorocarbonic ester, there will be formed
directly an acetjdenic ester :

E.C i eXa Cl.COoRi = XaCl + RC i C.CO„Ri
R and R^ may be identical or different, aliphatic or cyclic.

In the case of methyl hci^tine carbonate the equation becomes
CH3.(CH-.),.CiCXa + ChCOoCH^ =

CH3.(CH2).j.C : C.CO0CH3.

The order of procedure is therefore : —

(1) The preparation of an acetylenic hydi’ocarbon.

(2) The making of its sodium derivative.

(3) The subjection of this sodium derivative to the action of a
chlorocarbonic ester.

In the preparation of meth}'! heptino carbonate the starting
material is the ricinoleic acid existing in castor oil. When heated,
this acid gives an aldehyde containmg seven carbon atoms, that
is, cenanthol, also called heptanal, which is then to be chlorinated
bj’ means of phosphorus pentachloi’ide.

The resulting dichloride, saponified with potassium hydroxide,
gives heptine.

It is possible to represent tliis series of reactions b}’’ the following
equations : —

(A) Castor oil — > CigHgjOg -> CigHigGOoH (by-product)

Pvicinoleic acid Undocylenic acid

(B) CH3.(CH„)5.C0H -f PCI3

Heptanal

Dichlorlieptanc

I-

(D) CH3.(CH2),.C:CH

Heptine

(E) CH3.{CHo).,.C:CNa

Heptine Fodiuni

(F) CH3.(CH3),.C ; C.CO0CH3

Hclhyl heptine carbonate

A. Preparation of Ilcpfanol

CHa.fCHjls.COH.

313

PERFU MEB Y

Tlie decomposition of ricinoleic acid is effected by heating crude
castor oil (Kraft, Bericliie, 10, 2034 ; Erlenmeyer, Annalen, 176,
342 ; Jourdan, Annalen^ 200, 1020) in a distilling apparatus of
enamelled iron, using direct heat at 160° to 170° under a pressure
of 100 mm.

The heptanal, -which distils off together with a small proportion
of water, is fractionated under a pressure of 9 mm. The distilling
apparatus should be capacious, for there is considerable foaming.

The yield from tliis operation is quite small (10 to 12 per cent.),
and part of the undecjdenic acid becomes polymerised. Haller
has suggested that the decomposition be performed not upon
ricinoleic acid, but upon its esters.

B. Preparation of the Dichlor derivative

CH3.(CH2)5.CHCl2.

Into a dry vessel provided vuth a mechanical' agitator phos-
phorus pentacliloride is introduced. The vessel and its contents
are cooled to — 6° by a refrigerating mixture, the agitator is
started, and heptanal is introduced little by little, the temperature
being kept below 0°.

After all the heptanal has been added, the temperature is
allowed to rise, and the mass is then heated, stirring all the while,
until the reaction is completed. It is then cooled and poured
carefully into ice water. The oxycliloride of phosphorus dissolves
and decomposes, wMe the dichlor-compound formed is separated
by decantation, washed until free fi’om acid, dried with anliydrous
sodium sulphate, and rectified by vacuum distillation under a
pressm’e of 15 mm. The fraction coming over at 60° to 75° is
collected.

C. Preparation of Heptine

CH3.(CH2)4.C *: CH.

Originally, the saponification of the dichlor-derivative formed
by the preceding operation was effected by the use of alcoholic
potash (Behai, Bull. Soc. CJiim.., 49, 581, 888), but the 3deld was
unsatisfactory oving to a molecular transformation, wliich was
studied by Faworski {BericJite, 20, 781 ; 21, 1614; Kvaft, Jo^lr.
PraJet. Chem., 2, 37, p. 420) :

R.OHa.C : CH ^ B.O : CCHg.

Nowadays, in accordance -with the results of Degrez, the
saponification is performed by the use of dry pulverised potassium
hj'^droxide, with the aid of heat and at reduced pressure.

314

PEBFU MEB Y

The resulting product is poured into ice water, separated,
n-ashcd, dried carefully over anliydrous sodium sulphate, and
rectitied in a vacuum. The object of this rectification is to free
the heptine from chlorinated ethylenic hydrocarbons which
usually accompany it. (A complete separation by rectification is
difficult, if not impossible.)

The boiling point of crude heptine is 100° to 100° at 700 mm.

D. Preparation of Heptine Sodium

CH 3 .(CH 2 ) 4 .C : CNa.

The sodium derivative of the hydrocarbon is obtained by the
following method ; —

One kilogram of heptine, dissolved in absolutely anh^’drous
ether, is placed in a reflux apparatus provided with an agitator.
There is then introduced, little by little, 240 grams of sodium, in
fine wire, in the cold. The reaction, vigorous at first, slows down
toward the end, and is brought to completion bj’’ gentle heating
until the metal disappear.?.

E. Preparation of the Heptine Carbonate

CH3.(CHo)4.C:C.C02CH3.

The sodium having been entirely dissolved, a quantity of
anh3'’drous ether is added to the distilling apparatus, so as to
provide 10 parts of ether to 1 part of the sodium derivative. While
stirring, there is then added, little by little, 9 parts of methyl
chlorocarbonate. The mixture is left, while constantlj’’ stirx’ing,
for several hours, and slight heating is used to completo the
reaction. It is then cooled and the product decanted, washed
with water, and distilled through a fractionating column under
a pressure of 20 mm. The pure product boils at 107° under 20 mm.

In general, the homologues of methjd heptine carbonate [vert
dc I'iolctte) are prepared b 3 >- similar methods. This applies to com-
pounds differing ndth regard either to the acetylenic hj'drocarbon
from which thej'' are derived or to the radicle which is combined
with the acid.

The delicate point in these preparations is the making of the
lu'drocarbon. The starting material is an aldehyde or a ketone
which is easily' obtainable, either bj' sjmthesis or bj' some simple
chemical process from a natural source.

As examples falling within one or the other of these two classes
we maj" mention meth\*l isoamjd ketone, which is prepared by the
controlled decomposition of ethjd isobutylacetate ; methyl hexyl
ketono, which is formed b}* the oxidation of capr\’lic acid ; method

SI.?

PERFUMERY

lieptyl and methyl nonyl ketones, which exist respectively in
Algerian and in ordinary commercial oil of rue.

An important source of further compounds is the undecylenic
acid which is obtained as' a residual by-product in the manu-
facture of heptanal, the first stage in the preparation of methyl
heptine carbonate. This undecylenic acid may be esterified, trans-
formed into an alcohol by the method of Bouvault and Blanc, and
thence into an aldeh3’^de which maj'- serve as raw material for
acetjdenic derivatives of the same number of carbon atoms.

At the present time certain French houses are marketing the
following acetylenic esters : —

Heptine carbonates of methyl and ethyl.

Octine carbonates of method, ethjd, and amyl.

Decine carbonates of metl^d and ethyl.

Undecino carbonate of method.

The following esters of this series are known : —

Hydro-

carbon.

Source from *\v]iich
obtained.

Correspond-
ing ester.

Hoiling point.

Pentine

i\Ieth}d }?rop}d ketone .

Metbyl .
Btbyl
Isoam3d .

126°-127° at 24 mm.
93°- 94° „ 24 „
127°-128° „ 22 „

Isopeutine .

Isovaleraldeliyde

Metbyl .
Etbyl
Isobutyl .

68°- 69° „ 20 „
83°- 84° „ 19 „
99°-101° „ 19 „

Hexine

Meth}d butyl ketone .

Metbyl .
Etbyl .

91°- 93° „ 19 „
106°-108° „ 84 .,

Isohexine

Metbyl isoamyl ketone .

Metbyl .
Etbyl

98°- 99° „ 19 „
110°-112° „ 18 „

Heptine .

Ricinoleic acid .

Metlayl .
Etbyl
Isopropyl
Isobutyl .
Isoamyl .

107° „ 20 „
115°-116° „ 17 „
126°-127° „ 20 „
138°-139° „ 23 „
148°-149° „ 20 „

Isolieptine

Metbyl isoamyl ketone .

Metbyl .
Etb}d

98°- 99° „ 18 „
110°-112° „ 18 „

Octine

Metbyl bexyl ketone .

Metbyl .
Etbyl. .
Isopropyl
Isoamyl .

122° ,; 19 „
126°-128° „ 16 „
145°-148° „ 32
168°-172° „ 26 „

Isooctine .

Isobexyl metbyl ketone

Metbyl .
Etb}’!

122°-127° „ 31 „
135°-137° „ 30 „

Nonine

Metbylbeptenone .

Metbyl .
Etbyl

133°-135° „ 21 „
143°-146° „ 21 „

Undecino .

Metbyl nonyl ketone .

Metbyl ,

168°-172° „ 30 „

31C

PERFU MEBl

HEPTYL ACETATE. — ^Tliis ester has a floral-fruity odour.
Its specific* gravity is 0*S75 ; and hoiling point about 192°.

HEPTIX ALCOHOL. — ^Tliis alcohol, also knovai as cenanthyl
alcohol, is methyl-ainyl-carbinol, of the formula CH 3 CH( 0 H).
CHo.(CH 2 ) 3 .CH 3 . It is a liquid with a. powerful aromatic odour, '
and has been found occurring naturally in oil of cloves. It has a
specific gravity about 0-S32 at 15°, and boils at 175° to 170°. It
can be prepared from the corresponding aldehj'de, cenanthic
aldehyde (heptyl aldehyde), bj' melting sodium in diy hot
toluene, and well stirring until the paidicles arc in a minute state.
The mixture is then cooled in ice and the aldelyde dissolved in
acetic acid, and toluene is slowly added^ with continual stirring.
\^flien the reduction is complete, water is added and the toluene
layer separated, and the heptyl alcohol purified by fractional
distillation. Traces of it are used in artificial carnation perfumes.

HEPTYL ALDEHYDE.— See under Aldehydes, Fatty.”

HEPTYL FORMATE. — This ester resembles the acetate.
Its .specific gravity is 0*884: ; and boilmg pomt about 177°.

HEPTYL HEPTOATE.— This ester, CHaCCHals.OOC.CCHols
CH 3 , is of veiy powerful fruity odom*, and is one of the most
expensive of recent additions to synthetic perfumery.

HEPTYX VALERIANATE. — ^This ester has a ver 3 '^ fruity
odour. Its specific gravity is 0*8775 ; and boiling point about
244°.

HERABOL MYRRH.— See “MjTrh.”

HERABOLENE. — ^This bod}” is a tric^’clic sesquiterpene found
in the essential oil of herabol mjuTh. Von Friedrichs [Arch. dcr.
PJiarm.. 1907, 245, 208) found it to have the following characters : —

Boiling point (at 16 mm.)
Specific gravity at 20 °
Optical rotation
Refractive index

130-136°
0*943
- 14° 12'
1-5125

It 3 -icIds a dihvdrochloride melting at 99°.

HERACLEUM OILS. — The heracleum oils arc of interest
in that several of them contain the higher fatty alcohols and their
estens, substances which have reccntty become so important to
the up-to-date perfumer. Ilcradcum sjdiondylium is one of the
umbelliferous plants, loiown as the cow-jiarsnip. The fruit of

317

PERFU MERY

this plant yields from 0-5 to 3 per cent, of essential oil, having
the following characters : —

Specific gravity
Optical rotation
Refractive index
Acid value
Ester value

. 0-865-0-880

. 0° to + 2°

. 1-4260-1-4330
4-16
214-276

Zincke {Annalen, 1869, 152, 1) found the oil to consist mainly
of the caproic and acetic esters of normal octyl alcohol. Moslinger
{BericJite, 1876, 9, 998) examined two oils in wliich he found
ethyl butyrate ; a hexyl ester, probably the acetic ester ; octyl
esters, including the acetate, caproate, caprinate, and laurate.

Gutzeit {Annale7i, 1872, 163, 193) has examined the oh of
Hemdeum giganteum, in which he foimd ethyl butyrate. The oil
of the fruits of this plant has been examined by Sdiimmel da Co.
{Report, October, 1906, 41 ; April, 1908, 67) and found to have
the following characters ; —

Specific gravity
Optica] rotation
Refractive index
Acid value
Ester value

Ester value (after acetylation)

0- 8722-0-8738
+ 1° to + 1° 14'
1*4240

1- 6-3-7
281-288
311-314

HERNANDIA OIL. — ^Erom the wood of Eernandia peltata,
a plant known in Madagascar as faux camplirier , from 1 to
2 per cent, of an essential oil of powerful cumin odour has been
obtained. It was examined by Semmler and Zaar {Berichie, 1911,
44, 815), who found it to contain perilhc aldehyde (dihydro-
cumic aldehyde), myrtenal, cineol, and hmonene. Sdiimmel dd
Co, have examined the oil from several parts of the plant, with
the following results ; {Report, October, 1914 ; April, 1915, 51).
Eour samples of the trunk wood yielded between 1*03 and 2*06 per
cent, of oil having the following characters : specific gravity,
0*958 to 0*963 ; optical rotation, + 83° 45' to + 104° 12' ; and
refractive index, 1*4969 to 1*6011. Between 75 and 80 per cent,
of aldehydes were found in the oil. The root wood yielded 0*5 per
cent, of oil which had a specific gravity 0*9667 ; optical rotation,
-f- 126° 15' ; and refractive index, 1*5038. It contained 92*6 per
cent, of aldehydes. The oil distilled from the whole fruits (amount-
ing to 0*5 per cent.) had a specific gravity 0*963 ; optical rotation,
-f 50° 16' ; and refractive index, 1*4955. It contained 49 per
cent, of aldehydes. The almond-shaped kernels yielded 1*38 per

318

PERFU MEET

cent, of oil, of specific gravity 1'004:4 ; optical rotation, -f S7° ;
refractive index, 1*5061 ; acid number, 7-3 ; and ester number,
110-4.

HEXADECYL ALDEHYDE. — ^Tliis body is the normal 16
carbon aldehyde of the saturated fatty scries, of the formula
CHt(CH 2 )j^CHO. It is usuall}’ sold as “ Cig aldehyde,” or as
“ stravberry aldehyde ” on account of its marked odour and
flavour of ripe stravbcrrics. It is obtained from the methj'l ester
of palmitic acid by the same process as is undec3'lic acid {q.v) from
methyl laurate.

HEXENOL. — ^^Yalbaum [Jour. Prald.Gliem., ii., 06, 191S, 245)
has found this alcohol, in the form of its phenjdacetic ester, in
Japanese oil of peppermmt. It is an alcohol, of the formula
CH3.CH2.CH : CHlCHnlnOH, and has the following characters ;
specific gravity, 0-8508 ; optical rotation, — 0° 10' ; and refrac-
tive index, 1-4803. The phenylacetic ester itself, Cj^H^gOo, boils
at 299°, and has a specific gravity 1-000 ; optical rotation, 0° ;
and refractive index, 1-4981.

HEXINE CARBONATES. — See “ Heptine Carbonates.”

HEXYL ACETATE.— This ester, CH3(CH2)500C.CH3, ocem-s
m oil of Ilcradcnm giganicum. It is a liquid of fine fruity odour,
boiling at 170°, and having a specific gravity 0-890 at 0°.

HEXYL ALCOHOL.— Normal hexyl alcohol CH3(CH2)4CH2
OH is present in the oils of several species of heracleum, usually
in the form of liex^d butjTatc. It boils at 157°, and has a specific
gravity 0-820 at 20°. Isohexjd alcohol is present as its angelic
acid ester in oil of Roman camomiles. It boils at 154°, and has
a specific gravity 0-829, and specific rotation -f- 8-2°.

HEXYL BUTYRATE.— This ester, CH3(CH2)300C(CH2)2.
CH3 resembles the acetic ester, but has a more powerful fruity
odour. It is found in several of the heracleum oils, and in the oil
of Tlicohroma Cacao.

HEXYL FORIMATE. — ^This ester closety resembles hcptyl
formate. Its specific gravity is 0‘8S8 ; and boiling point 154°.

HEXYL VALERIANATE. — This ester closcty resembles the
corresponding hcptyl ester. Its specific gravitj- is about 0'870 ;
and boiling point 224°.

HEXITENIC ALDEHYDE. — See under “ Aldchvdes,
Patty.”

319

PERFUMERY

HIBISCUS ABELMOSCHUS.— See “ Ambrette, Oil of.”

HINOKI WOOD. — ^TlieHinold tree, Ohaemcecyparis obkisata,
grows freely in Japan, and thrives exceptionally well in the
nionntainous districts of Formosa. The wood yields about
2*4 per cent, of an essential oil with a thujone-like odour. It has
a specific gravity 0'8S2 ; specific rotation, + 50-37° ; and refrac-
tive index, 1*4990 at 18*5°. It contains pinene and cadinene, and
a small quantity of odorous oxygenated constituents not yet
identified.

HOMOHELIOTROPIN. — ^This substance is not a commer-
cial article, but has been produced in the laboratory as a pale
yellow oh of agreeable heliotrope odour. It has a specific gravity
1*265 ; refractive index, 1*5547 at 15° ; and boils at 133° at 8 mm.
pressm-e. It is prepared by passing ozonised air into a solution of
safrol m dry acetic acid, and reducing the ozonide so formed bj’
means of zinc powder {Jour. Chem. Ind. Japan, 1922, 25, 1409).

HOMOLINALYL ACETATE.— This ester, of the formula
CjiHioOOC.CHg, is an oil of sweet bergamot odour, boiling at
about 115° at 15 mm. It is prepared bj'" the action of homolinalol
sodium on acetyl chloride.

HOMORANTHUS OIL. — Homoranilms flavesems is a
slirub grovsing freely in certain parts of New South Wales.
Penfold {Jour, and Proc. Roy. Soc. of N.S.W., Ivi., 1923, 197)
has investigated its essential oil, wliich is of particular interest in
that it is the only Austrahan essential oil found, so far, to contain
the olefinic terpene, ocimene, which is present to the extent of
about 80 per cent. The oil, w^hose earlier fractions have a powerful
odour of bananas, is yielded to the extent of 0*35 to 0*82 per cent.
It has the following characters : specific gravity, 0*8206 to 0*8429 ;
optical rotation, — 1° 75' to + 2° ; refractive index, 1-4836 to
1*4873 ; saponification value, 8 to 45-9 ; and saponification value
after acetylation, 51 to 85-4.

On distillation at 10 mm. tlu’ee crude oils yielded fi’om 81, to
85 per cent., distilling below’ 77° at 10 mm., wliilst the last two
consignments gave 16 to 18 per cent., distilling between 123° and
142° at 10 mm. The first lot gave 11 per cent., distilling betw^een
72° and 120°, 12 per cent, between 120° and 160°, leaving a
resinous residue of about 14 per cent., which no doubt partiaU}’’
accounts for the high ester and alcohol numbers.

Determinaiion of d-a-Pinene. — ^Repeated fractional distillation
at 20 mm., using a six-disc column, of the portion of oil boiling

320

PERFVMERl

below 77° at 10 mm. resulted in the partial separation of a
small quantity of de.xtrorotator}’’ constituent distilling below

15 °

70°. It had specific gravity at -pr, 0-S313 ; optical rotation

J. o

from -f S-7 up to + ; refractive index at 20°, 1*4746.

It consisted of d-a-pinene together with ocimene, and readily
gave a nitrosochloride, which on pirrification melted and decom-
posed at 109°.

Determivation of Ochncnc. — ^iMany repeated fractional distilla-
tions conducted at 10 and 20 mm. were made, but it was found
extremely difficult to remove the associated dextrorotatory
terpene, indentified as d-a-pinene, despite the high content of
the olefinic terpene. The best samples separated possessed the
following characters : —

Boiling point at 10 mm.
Boiling point at 20 mm.

15°

Specific gravity at

Optical rotation
Bcfractive index at 20°

G7°-68°

75°-7G°

0*8034

0° to 4- 0 3°
1-4857-1-4859

Its identity was established by the following experiments : —

(1) The readiness until which it absorbed oxygen when spread
on a watch glass. Instead of volatilising in the manner of a true
terpene, it readily yielded a tacky resinous mass, which gave
highly’ refracting emulsions with alcohol or water.

(2) On subjecting a sample of boiling point 74° to 75° at
20 mm. to distillation over sodium at 757 mm., the first drops
came over at 172°, onc-thii’d of its volume distilling at 173° to
175°, tlic remaining two-thirds boiling between 175° to 182°,
thus showing partial conversion into allo-ocimcne.

(3) On reduction with sodium and alcohol, diliydronnwcene
was obtained in a moderate^ pine condition, possessing the
following characters : boiling point, G8° at 20 mm. ; optically

15°

inactive ; specific gravity at — , 0*790

refractive index at

20°, 1*4511.

(4) The bromide of the above dilnffiromyrccne was prepared
by dissolving the hydrocarbon in a mixture of 1 part ami'l alcohol
and 2 parts ether, as recommended in Parr\*’s “ Cheini.stry of
Essentia! Oils,” vol. ii., page GS. On recrystallising from boiling
alcohol it melted at 88° to 89°.

Dctcrminalton of Sesquilcrj}cne. — ^Tlie fractions boiling above
t- S21 -I

PBRFU MERY

120° at 10 mm. were redistilled, finally over metallic sodium,
but the quantity available did not permit of the isolation of the
sesquiterpene in anything like a condition of purity, with the
single exception of the last distillation. This was partly accounted
for by the presence of resinous bodies in the first two lots, which
is evident from the following table : —

Boiling point.

Specific gravit 3 %

Optical

rotation.

Hefraclive
^ index at
20°.

26/9/21

18/10/21

21/8/22

136° Lo 110° at 5 mm.
127° „ 110° at 5 „
133° „ 135° at 10 „

0'9192 (17°)
0-9333(18°)
0-9230 (15°)

— 7-3°

— 1-6°

— 4-25°

1-5008

1-5018

1-5010

The last mentioned is as pure a sample as was possible to be
obtained.

Minor ConstHnents.—^moW quantities of am}*! alcohol and its
acetic and butyric acid esters were identified.

HONEYSUCKLE. — The woodbine, of which there are numer-
ous species, is Loniccrd Pcriclynicnmn (or other species), belonging
to the natural order Caprifohaccce. It is a favourite climber,
whose flowers have a delightful fragrance. According to D.
McDonald (“ Fragrant Flowers and Leaves,” 1895, 71) the following
are the principal species of lonicera with fragrant flowers : —

E. pcriclymcnuni, with large creamy flowers, blooming early in
the year, and with a perfume which is most noticeable in the early
evening.

L. sGrotinum. — This has reddish flowers, blooming late in
summer and in autumn.

L. caprifolium. — Tliis is so called because goats are said to be
fond of its leaves.

L. JragrcLniissiina, — This plant bears fine white, fragrant flowers
about February.

L. hrachypoda . — This is known as Chinese honeysuckle. It bears
yellow flowers from May to October.

L. semper vivens.—Y\\\Q is a cultivated ornamental climber
known as trumpet honeysuckle.

It is very rare that any preparation of honej’^suckle flowers is
to be found on the market. The fancy perfumes sold under the
name honeysuckle are entirely artificial, and do not actually
reproduce the natural odour. para-Cxesoi derivatives, phenyl-

322

PER F u

acptic aldehyde, linalol, goraniol. storax, and similar mixtnrcs arc
tised, to %vhicli a floral note is given b}’ the addition of a little
true Hover oil, such as jasmine, etc.

HOPS. — ^The hop is IJumithis lupitlus. one of the Canna-
linacccc. It and its essential oil are used principally for flavouring
purposes, but very small quantities are occasionally used where
a special ” note ” in a perfume is required. Hops, which are
themselves fairly expensive, only yield from O-S to 1 per cent, of
essential oil, which is very costh'. It contains a sesquiterpene
which Chapman {Jour. Clicm. Soc., 1903, S3, 505 ;. 1895, 67, 54
and 780) considers to be a new body and which he termed humu-
Icne, but which Deussen (Jour. Prald. Clicm., 1911, ii., S3, 483)
considers to be a niLxture of the isomeric caryophyllenes. Rabak
(Jour. AgricuK. Research Depi. of Agriculture, Washington, 1914, 2,
115) has also isolated formic, valerianic, and heptylic acids in the
free state, and fonnic, acetic, octylic, nonylic, decylic, a;nanth3dic,
and butyric acids in the form of esters. IMjT'cenol and its esters
are also j)rosent. Rabak (Zoc. cit.) gives the following as the
characters of pure hop oils of various origins ; —

Origin.

Year.

Yield

per

cent.

Specific

gravity.

Refractive
* index.

Acid

no.

. .

Ester

no.

Solubility
in 94 per
cent,
alcohol.

California

1907

0-24

0-823

1'4856

2-3

44-4

5'4 vol.

1903

0-836

1-1738

1*7

45*5

4 „

1909

0-38

0-839

1-4730

1-8

16-8

3-6 „

Oregon .

0-20

0-8343

1-1802

1-6

57-0

4-6 „

1908

0-32

0-838

1-4730

1-0

50-2

3-3 „

0-30

0-8133

1-4705

2-8

56-0

3 ,,

Kew York

1907

0-16

0-862

1-4801

3-6

Btra

3-5 „

1908

0-14

0-837

1-1756

2-1

BnSI

3-5 ,,

1909

0-15

0-8777

2-5

51-8

3-7 „

AYasliington

1908

0-36

0-850

1-4763

51-8

3-5 „

1909

0-38

0-8464

1-4734

I '5

53-8

3-3 „

Saaz (Bohemia)

1907

0-32

0-855 1

1-4905

1-5

52-8

! 4 n

1908

0-23

0-824

1-4852

1-0

52-S

6 „

•

0-861 '

3-0

55*3

4 „

HOUND’S TONGUE. — ^This is the popular name for
Liairis odoratlsshna, an odorous plant whose leaves contain
coumarin, growing in the savannahs of North Carolina to Florida.
(See “ Liatris odoratissima.”)

32.'?

21— s

PERFTJ MER Y

HOUTTUYNIA CORDATA.— This plant is known in
Japan as Dohudame, and, according to Shinosaki {Jour. Ghem.
Ind. Japan, 1921, 24, 557), the whole herb yields, on distillation,
0*005 per cent, of a brownish essential oil having a specific gravity
0*8744 ; specific rotation, — 5° ; refractive index, 1*4685 ; acid
number, 16*65 ; and saponification number, 28*4. It contains
methyl-nonyl-ketone and an afiphatic terpene, wliich is probably
myrcene.

HUMULENE. — ^This sesquiterpene {vide “Hops”), which
may be identical with caryophyllene, v/as isolated from oil of hops
by Chapman {Jour. Cliem. Soc., 1895, 6*?; 54, 780). It is an oil
of specific gravity 0*900 at 20°, and boils at 263° to 266°. Deussen
considers that this sesquiterpene is identical with caryophyllene
{Jour. Prakt. Ghem., 2, 83, 483).

HYACINTH. — ^The hyacinth, HyacintJius orientalis, belong-
ing to the natural order Liliacece, is a native of Syria and other
districts of western Asia. According to Poucher (“ Perfumes and
Cosmetics,” p. 222), it was introduced into Great Britain dming
the sixteenth centurj’-.' It was then only a single-fiowered plant,
but during the seventeenth century double-flowered plants began
to appear. The plant is to-day cultivated on a large scale in
Holland, particularly in the neighbourhood of Haarlem, which is
one of the principal centres of the Dutch bulb growing industry.
The odour of hyacinths is sweet and heavy, and if m a confined
space, often overpowering. The natural perfume is available in
the form of a concrete or an absolute, but the essential oil is not
a commercial article (see P. ds E. 0. R., 1912, 77). The perfumes
of different varieties of the flower vary considerably amongst
themselves, some types having a rather impleasant odoui’.
Generally spealdng, the odour of the paler-coloured flowers
is more deficate than that of the darker varieties, and single
flowers .usually give a better yield of concrete essence than double
ones.

Enklaar {Ghem. Weekhlad, 1910, 1) obtained a small amount
of the essential oil by extracting the flowers with benzene, distilling
ofl the solvent at low pressure, precipitating waxy matter with
dilute alcohol, and again distilling. The yield was only 0*016 per
cent, of the weight of the flowers. The oil itself is of rather
unpleasant odour rmtil heavily diluted. On washing it with
dilute alkaline solution, traces of sulphuretted hydrogen were
removed from it. The oil was fractioned at 10 mm. pressme and

324

PERFUMEB Y

into three fractions : (1) boiling below 90°, (2) boiling
botv'(,c.’n ‘.'2'' and Q-r^ and (3) boiling from 9i° to 150'’.

Tiif liivt fraction wn*? found to contain a rcry volatile snb.^tanec
of di'’grceatilr> odour, which has not been identified. In the

second fraction a body wa.'^ found, po.-'^ibly of the formula CuITopO,
having the following characters ; siiecific gravity, 0*907 ; rcfrac-
tu'C index. 1-40J4 .at 10° ; boiling point, 205° to 20G° (92° to
94° at 10 mm.) : and optical rotation, -r 1° o2'. Fraction (3)
was found to contain benzyl benzoate, and probably free benzyl
alcohol and cinnamic acid esters. Tracc.s of vanillin and freo
benzoic acid are also probably present. A fluorescent basic
substance, free from nitrogen, was found, but mcth 3 'l anthranilato
was absent. The oil contains about 20 per cent, of esters, 1 per
cent, of free alcohols (benzyl alcohol ?), and 5 per cent, of the
. fluorescent substance mentioned above.

TJic majority of the perfumes sold under the name h3'acinth
to-daj* are cither entirely or almost entireh’ artificial. Into most
of them several constituents usually enter. Xearlj’’ all of them
contain a little tcrpineol {q.v.). The following compounds are also
largely employed : —

o-Phenylchloreth 5 dene and n-phen 3 d-brometh 3 deno (bromo-
slyTolcne) *are prepared from cinnamic acid. The former was first
prepared b 3 '- Stenhouse b 3 ’' distilling cinnamic acid with bleaching
powder solution.. It is formed b 3 - passing chlorine into a solution
of cinnamic acid in carbon disulphide and decomposing the phcn 3 d-
dichloro-propionic acid thus formed by boiling with water.
<7-Phen3dchloreth3*Ienc boils at 199°.

Bromost3Tolenc or n-phcn3d-brometh3*lene is formed when
phcn 3 *ldibromopropionic acid is boiled with water. This acid is
prepared b 3 ' dissolving cinnamic acid in carbon disulphide and
gradualh' adding a solution of bromine in carbon disulphide. It
cr 3 'stallises in plates melting at 195°. On boiling with water,
a)-bromost3Tolcne is formed, which boils at 219° to 221° and melts
.at 7°.

Cinnamic alcohol, formcrl 3 ' called st 3 *ronc, is found in st 3 Tax
and balsam of Pern.

It can bo prepared b 3 * Eaponif 3 ’ing cinnam 3 ’I esters with potash
and steam distilling the product. S 3 'nthcticall 3 ' it is obtained by
reducing cinnamic ahlch 3 'de.

It is a cr 3 'stallinc compound when pure, melting at 33° and
boiling at 25S° ; its specific gravity is 1*010 to 1*030 at 35°. It is
soluble in dilute alcohol, and can thus be separated from alcohols

PEBFU MERY

of the geraniol type. On oxidation it yields cinnamic acid melting
at 133°, and by further oxidation benzoic acid is formed.

Phenylacetaldeh 3 '’de is the newest, and perhaps the best, of the
artificial hyacinth odours. It is prepared b}'' heating phenyl-chlor-
lactic acid with alkalies. When pure, it has a specific gravity of
1-085, boils at 205° to 207°, and has a refractive index of 1-5253.

HYDROCARBONS, DETERMINATION OF.— The deter-
mination of terpenes and sesquiterpenes in terpeneless oils is a
matter of considerable importance, especially in terpeneless lemon
and orange oils. The only process which yields at all accurate
results is that of Bocker {Jour. Praki. Cliem., 1914, ii., 89, 199).
This will be found described under “ Lemon Oil.”

HYDROXYCITRONELLAL. — This recently introduced
synthetic perfume is a mixture of at least two bodies, hydroxy-
citronellal and diliydroxycitronellal. The commercial article has
a specific gi’avity about 0-955, optical rotation about -}- 7°,
refractive index about 1-4530, and boils at about 115° to 135° at

10 mm. It is of great value in all perfumes of the hly type.

HYDROXYGOUMARIN.— See “ Umbelliferone.”

HYDROXY-METHOXY-CYMENE.— This phenol, CnHicOa
(probably), occurs to theextent of 0-2 percent. inCyprian origanum

011 (Pickles, Bull. Imp. Inst., 1906, 4, 297).

HYPNONE. — ^This is another name for acetophenone {q.v.).

HYPTIS SUAVEOLENS. — ^This is an aromatic plant
wliich is found from Mexico to southern Brazil, and also in the
Philippine Islands, Java, Cliina, and the East Indies. The leaves,
when dried, are sometimes used as an adulterant of patchouli
leaves, so that the resulting patchouh oil vdll be, pro tanto,
adulterated with the oil of hyptis. According to Bacon {Philippine
Jour. Sc., 1909, 4, A, 130), the plant, which is known in the
Philippines as suheabayog, 3aelds 0-0135 per cent, of a greenish
essential oil vith an odour of menthol. The natives of Java know
the plant as daon roeroskee cetan. Menthol appears to be -the chief
odorous constituent of the oil. Hyqjtis spicaia 3nelds an oil con-
taining menthone and pulegone {BchimmeVs Report, April, 1904,
96). Hyptis Salzmamii yields an oil of specific gravity 0-904,
having a pleasant odour of camomile and balm, and Hyptis
fasciculata yields one of specific gravity 0-905, having an odour
of balm and origanum oils.

HYSSOP, OIL OF. — ^The ordinary hyssop, Hyssopus

326

FERFU MER 7

ojricb'.r.lis, is a labiate plant indigenous to the 3Iediten‘ancan
coun::ic 3 and Central Asia. It grows wild in the hills of
Danplune and on the plains of Provence. LiJce lavender, it
prefers chalky hills and dry light soil. It is particularly abundant
in fhc covs'iovs of La. Fossette a.nd Lo Petour, where it flowers in
Sepfemoer and October, when it. is gathered for distillation. It
is also found in the Savoy, Le Bugc}'', Le Cher, and La Nievre.

Ihc flowers are of a pale colour, varying from blue to white
and ro.=e, and arc verj* odorous. Apart from its odour value,
hyssop is esteemed for flavouring purposes, and is said to be an
ingredient in some of the famous French lirpieurs.

Hyssop is easily* cultivated, and from 1,500 kg. of the wild herb
about 7-0 leg. of essential oil are obtained. This is a pleasantly
aromatic liquid with a sweetish odour. Its characters are as
follows ; —

Specific gravity . . . 0-92.5-0-94r5

Optical rotation . . . — 12° to — 25°

Refractive index . . . 1-1730-1-4SG0

Acid value .... 1-2

Edcr value .... 3-16

Ester value after acetylation . 35-48

Jcancard and Satie, however [American Ferf inner. 1909, 4, 84),
report on two samples distilled in Cannes from the fresh floAvering
herb, which had the followdng characters : —

1 . 2 .

Specific gravity .

0-9252

0-9262

Optical rotation .

+ 1°

- 2° 6'

Acid value

0-8

E'ter value .

9-2

11-9

Ester value after acet 3 da-
tion.

51-1

According to Gildemeister and Kohler [Wallacli-Fe-stscliriJl
GoUingen, 1909, 414 ; Schimmel’s Report, April, 1908, 57 ; October,
1909, 69), oil of hyssop contains jS-pinene, a high-boiling alcohol
(boiling point, 221° to 222°), and sesquiterpene derivatives. The
most interesting substance present, however, is a body which has
been named f-pinocamphone, and which has not been found in
any other essential oil. This body is present to the extent of
about 50 per cent, of the oil. It has the following characters ; —

Formula

Boiling point.

Specific gravity

Optical rotation
Refractive index

CinHieO

212°-213°at752mm.

0- 9CG2

— 13° 42'

1- 4742

327

PERFU MER Y

It forms a semicarbazone melting at 228° to 229°, and a
dibromide melting at 93° to 94°. On reduction it yields a crystal-
line alcohol melting at 218° and having an odour of camphor.

Agastaclie pallidijJora, the so-called Great Hyssop, one of the, .
labiate plants widely distributed throughout the mountainous
regions of the Far West and Pacific coast of the United States,
yields an essential oil entirely different from true hyssop oil.
The following interesting account of this oil is by J. F. Couch.
(See P. c& E. 0. R., 1922, 177.)

The material which was used in the following experiments was
obtained at the experiment station of the Bureau of Animal
Industry, at Salina, Utah, situated at an altitude of about
8,000 feet, in the Wasatch Eange. The attention of the investi-
gator was first directed to this plant by the very intense, fragrant
odour which diffuses tlu’ough the air in its neighboiu’hood, and
he describes his experiments with it in the American Journal
of Pharmacy. Before the blossoms of the plant have opened the
odour noted resembles that of th-^one ; after blossoming the
odour is more lilce a mixture of thjune and peppermint. The
leaves of the plant bruised between the fingers develop a strong
thyme odour ; the flowering heads subjected to the same treat-
ment 3 deld an intense peppermint odom with a small thyme
component. It was therefore thought of interest to investigate
the essential ofl, of this plant as a possible som’ce of thymol or
menthol.

Accordingly several collections of flowering heads and of leaves
were made 'and the fresh material was immediately, except for
one experiment, subjected to steam distillation. The quantities
used and the yields of dry oil were as follows : —

Per cent.

July 28. 3,720 grams flowers yielded 6*84 grams oil . 0T84

Aug. 5. 2,560 grams flowers’yielded 3*96 grams oil . 0T55

Aug. 11. 3,500 grams flowers 3 deld; d 11-06 grams oil . , 0-316

Aug. 17. 950 grams leaves jneldcd 0-79 gram oil . 0-083

The first flowers collected were just beginning to open, and full
maturity was not attained until about two weeks after, when the
third lot was collected. This probably accounts for the larger
yield of oil from the lot of August 11th. The lot of August 5th
was ground tlirough a meat chopper and allowed to stand over
night before distilling. Contact with the air turned the ground
material deep brown, possibly through oxidation of some phenoHc
gonstituent. The leaves used were carefully separated from ihe

328

PERFU 21 ERT

stems of the plant. These stems are coarse and fibrous, and do
not appear to contain oil. TIio leaves were then ground through
the meat chopper and steam dhstilled.

The oils obtained from the flowers all carried a very pene-
trating peppermint odour with some marked suggestion of thyme.
Thej' were slightly j’ellow. The oil from the leaves had a rank
thyme -odour on!}’. Kone of the samples of oil. nor any of the
aqueous distillates containing dissolved oil, aflccted ferric chloride
solution and all were neutral to litmus.

The following physical constants were determined for the oil
from the flou’ers : —

Density at 20° .... 0-91024

Specific rotatory poAver at 25° . . — 8-60°

Judex of refraction at 25° . . . 1*4805

The oil is soluble in the ordinary solvents. On cooling to
— 10° and letting stand at that temperature for several hours
there was no separation of anj’- crystalline material. Conse-
quently, the amount of free menthol, if anj’, present cannot be
very large. Phenols were tested for b}’’ the usual absorption
method, using 5 per cent. NaOH. The volume of the oil dimi-
nished slightly, but on acidifying and shaking out the aqueous
layer with ether, no phenols Avere found. Pulegone and other
ketones were tested for and found absent.

lANTHONE. — ^lanthone, CjcH2.,0, is a ketone of the ionono
type, resulting from the condensation of citral AA-itli mesit}'! oxide.
It has a strong Ariolet odour, resembling that of iononc. It boils
at 101° at 10 mm. pressure.

The pscudo-ianthone produced in the condensation is an oil
haA'ing but little odour of violets, boiling at 180° to 185° at 10 mm.
This is isomcrised to ianthone by dilute sulphuric acid.

IDENTIFICATION METHODS FOR PERFUME CON-
STITUENTS. — It frequcntl}’' becomes of importance to the
perfumer to examine compounded perfume materials in order to
obtain ns much information as possible in regard to their com-
position. Examinations of this nature require a very considerable
amount of skilled knoAvIcdge and experience, and are often of the
nature of a prolonged research.- The separation of constituents
in a mixture of, for example, natural isolates and sj-nthetic per-
fumes may often be effected by physical method.s, so that the
determination of the usual con.stants of the separated con'^titnent

329

PERFUMER Y

may be sufficient to enable an identification to be made. But
it is very often necessary to convert the separated constituent
into one or more of its crystalline compounds, the melting point
of which enables the original substance to be identified with
practical certainty.

The follovdng are examples of typical methods for preparing
such crystalhne compounds : —

(1) Hydrocarbon Constituents. — A number of the terpenes form
characteristic crystalhne derivatives, such as the nitrosochlorides,
the bromides, and other compounds.

To prepare the nitrosochlorides, the terpene, or a fraction rich
in the terpene, is dissolved in tluree times its volume of petroleum
ether and cooled to 0°. An 8 per cent, solution of nitrosyl chloride,
in equal volumes of chloroform and petroleum ether, is gradually
added vdth constant stirring, care being taken that the tempera-
ture does not rise much above 0°. Alcohol is then added, and the
crystalline precipitate is separated and recrystallised from warm
chloroform. Or 5 parts of the terpene, 7 of amyl nitrite, and 12
of glacial acetic acid are mixed at a temperature of 0° or lower,
and a mixture of 6 parts of hydrochloric acid and 6 parts of
glacial acetic acid, also cooled to 0°, gradually added with con-
stant stirring. Five parts of alcohol are then added, and the
mixture is allowed to stand in ice and salt for a time, when a
crystalline mass separates out. Tliis is pm’ified by separation,
washing with alcohol, drjnng, and recrystaUising from chloroform
or ether, as may be necessary.

The bromides of unsaturated terpenes are prepared, e.g., in the
follo'wing manner. The terpene or terpene fraction is dissolved
in four times its volume of glacial acetic acid, and the mixture
cooled in ice. Bromine is then added, drop by drop, so long as it
becomes immediately decolourised. The mixture is allowed to
stand until crystals separate. These are filtered off, dried on
porous paper, and recrystallised from acetic ether.

(2) Alcohols . — ^The most important crystalline derivatives which
serve for the identification of alcohols are the phenyl-urethanes
and the acid phthahc esters. (See also under “ Alcohols.”)

To prepare the phenyl-urethanes the following method may be
used. The alcohol is mixed with SO per cent, of its weight of
phenyl isocyanate, and allowed to stand in a cold place until
crystallisation has taken place. The crystalline mass is pressed
between porous paper and recrystallised from petroleum ether or
ether, as may be necessary.

330

PERFUMERY

The acid phthalic esters may he prepared by mi>dng tlic alcohol
■noth about an equal -weight of phthalic anhydride and half its
■w’cight of dry benzene, and heating the mixture under a reflux
condenser until it becomes homogeneous. This operation should
proceed for an hour, the temperature being slowly increased up
to 180° to 190°.

When the mixture is cold, it is shaken with water and dilute
solution of caustic soda added until it is very faintly alkaline,
using phenolphthalein as indicator. The mixture is then extracted
tu-ice with ether, acidified with dilute sulphuric acid, and the solid
ester filtered off, dried, and recrystallised from dry benzene.

( 8 ) Aldehydes and Kcioncs. — ^The oximes, scmicarbazones, and
phenyl-lmlrazones are the most frequently prepared ciystallino
compounds of the aldeh 3 'dcs and ketones. For the preparation
of the oximes equimolccular quantities of the aldehj'de and
hydroxA-lamine are heated in alcoholic solution on a water bath
for an hour under a reflux condenser. The hydroxylamine is
usually added in the form of its hj^drochloride, and liberated by
means of alkali. For example, 20 grams of camphor are dissolved
in 50 c.c. of 95 per cent, alcohol, and 15 grams of lydro.xylamine
lydrochloride added, and then 15 grams of sodium bicarbonate.
The mixture is heated under a reflux condenser for one to two
hours, and cooled, diluted ^vith water, and the oxime thus pre-
cipitated collected, dried, and recr.ystallised from petroleum ether.

The scmicarbazones arc usuallj’- obtained b 3 ’' dissolving the
aldclyde or ketone in alcohol and adding an equimolccular mLxturc
of semicarbazide h 3 ’^drochloride and acetate of sodium. The
mixture is allowed to stand for a time with occasional shaking,
and the scmicarbazone is precipitated with water. It is then
rccr 3 'stallised from hot meth 3 d alcohol.

The phen 3 ’lliydrazones are usually prepared by acting on the
aldehyde or ketone with a dilute solution of phenylhydrazine in
acetic acid. For example, 10 parts of freshly prepared phen 3 l-
In'drazinc are dissolved in 5 parts of acetic acid, 1 part of the
aldelyde added, and the whole heated on a water bath for half
an hour. The mixtmre is allowed to stand for twelve to twcnt. 3 "-
four hours, when the precipitate is filtered off, dried, and recr 3 -stal-
liscd from benzene.

For a number of other useful compounds for identification
purposes and their preparation, sec “ The Analy.^is of Perfumery
and riavom-ing S 3 'nthetics and Isolates,” b 3 ' T. H. Durrans
(P. cO E. 0 . P., 1924, 219).

331

PERFUMERY

IDESIA . — Idesia Poly car pa, also known as Polyearpa Maxi-
mowiczii, is a large-growing J apanese tree belonging to the Bixinece,
bearing highly odorous flowers, which are used locally for perfume
purposes, although the joerfume is not extracted from them.
Then’ odour is somewhat heavy, but exceedingly sweet,

ILLURIN BALSAM. — See “ Hardwickia Balsam.”

IMPERATORIA OSTRUTHIUM, OIL OF.— This oil is
distilled from the root of the plant, which is also knoAvn as master-
wort. It is a plant indigenous to the mountainous regions of
central and southern Europe. The yield is about 1 per cent, of
an oil of characteristic aromatic odour, and having a specific
gravity 0-876 ; optical rotation, + 66° ; and boiling at from
170° to 190°. Lange (“ Year Book of Pharmacy,” 1912, 100)
has examined an oil distilled from two-year-old Tyrolese plants,
which yielded 1 per cent, of essential oil. This oil had the foUowmg
characters : —

Specific gravit}^ .... 0-8627 at 20°

Optical rotation . . . . -j- 59° 30'

Acid value ..... 0-8

Ester value . . . . . 17-9

Ester value after acetylation . . 28-4

Esters of isobutjnic, isovalerianic, isopropylidene-acetic, formic
and acetic acids were present, together with terpenes and
sesquiterpenes.

INCENSE. — ^This substance, used for ecclesiastical purposes,
is a perfume material of considerable antiquity. According to
Exodus XXX., 34-36, the formula for the substance used in the
time of Moses for Jewish ceremonial pm'poses is as follows : “ Take
unto thee sweet spices, stacte, and onycha, and galbanum, these
sweet spices, with pure frankincense : of each shall there be a like
weight : And thou shalt make it a perfume, a confection after
the art of the apothecar}’-, tempered together, pure and holy : -
And ,thou shalt beat some of it very small and put of it before the
testimony in the tabernacle of the congregation.” According to
“ Pharmaceutical Formulas ” (8th ed., p. 228), all these constituents
are known with the exception of onycha. A lengthy correspondence
in the Chemist and Druggist, August 26th, 1899, and following
issues showed that in the Hebrew it seems almost conclusive that
onycha denotes the crustaceous covering of the shells of certain
species of univalve shell fish found in the Red Sea and the Indian
Sea ; but there are also reasons for supposing that a 'high grade

332

PERFUMERY

gum benzoin was the substance in question. E. i\I. Holmes .siated
that a Jewish recipe for the incense used before the destruction
of the Temple (incense not now being used iir Jewish ceremonial)
included as the chief ingi-cdients, balm, onycha, galbanum, frank-
incense, and in lesser quantities, m^Trh, cassia, spikenard, saffron,
costus, canella, cinnamon, soap of Carsina, and “ a herb fitted to
I'aise a fume.” The onj'cha was to be refined In* means of the soap
of Carsina, and rendered more powerful by digestion in wine of
Cyprus. It is therefore quite apparent tliat the exact composi-
tion of the Levitical incense is unknoum, but the following are
average specimens of the incense used b\' the Roman and Anglican
cluirches : —

Drachms.

01ib.anum . .16

Benzoin . . 11

Cascarilla bark . l”
Storax . . 1

Drachma.

Olibanum .

. 20

Bonzoiir

Cascarilla bark

Cassia bark

Cloves

The principal gum resin xised as the basis of incense is olibanum,
or frankincense. (See under “ Boswellia Resins.”) In addition
to this substance, African bdellium is known as African incense.
(See under “ Bdellium.”) African bdellium is mostly derived
from Comm'i])ltora ajricana. The tree flourishes in the grassy
plains of Abyssinia and the Sudan, and is knovm to the natives as
Oanka. According to Rangon [La Parjumcric Moderne, 1023, 103)
the bdellium is gathered from December to jMa3\ The natives
make eight or ten incisions in the trunlc of the tree, and the white
liquid which exudes soon turns j’cllow, and dries in the form of
small tears. The}* are then detached with a metal instrument,
softened by exposure to the sun, and the debris picked out. A
third gum resin, which is known as incense gum, is the so-called
incense of India, which is the product of BosicclUa serrafa. (See
“ Boswellia Resin.”). The incense gum described by Avicenne
under the name Koondar is sold in the bazaars of the Bombay
Presidency under the names Dup Salai or Gunda hiroza.

The frue “incense,” the incense of Arabia, or olibanum,
although obtained in the main from BosivcUia Cciricrii, al.'jo con-
tains the product of other species. According to Birdwood and
Eliickiger, three varieties are to bo distinguished. Of these
“ Luban Bedowi ” or “ Luban Makur ” is the product of Bostrdlia
Carlcrii, and is known to the natives as “ ilohr meddu ” {mah
franl’ivccnsc ; Mohr Madow, Duhan Dakar — see under “ Boswellia

333

PERFUMERY

Resin ”). “ Luban Sheheri ” is the produet of BoswelUa Bhan-

Dajiana, and is the “ Mohr add ” of the natives. And, lastly,
“ Luban Mati ” or “ Luban Me3^eti ” is the product of BoswelUa
Freearana, and is also known as female Jranhincense.

These native names must be accepted vdth some caution, as
they are often applied loosely to products whose origin is not
positively known to the natives.

In the Antilles and in Guiana exudations from forest trees, such
as Proiium liepiaphyllum, belonging to the natural order Burse-
racece, are knorni as incense, but these appear to be elemi or
tacamahac resins. The white incense is produced by Protium
hex)iapMjllum and Proiium aliissimum, whilst the so-called Caj’-enne
incense is produced by Protium guianense. On the west coast of
Africa several species of Daniellia, giant trees of the Leguminosce,
are known as incense trees.

INCHI GRASS OIL. — ^The Indian grass Cymibopogon
ccesius is closclj’ related to Cymhopogon Martini, but is un-
doubtedl}'- a different grass. Where the two grasses meet, tran-
sition forms occur. The essential oil had not been carefully
investigated until 1922, and as the grass is common in certain
districts of India and the essential oil is liighl}'- odorous, resembling
palmarosa oil, it is possible that it ma}’- soon become of commercial
importance. The following interesting account of the grass and
oil is due to Moudgill and ICrishna Ij^er (see P. cb E. 0. R., 1922,
292), and is reproduced fuUj’-, as it has not yet appeared in any
text-book : —

Inchippul or Sulclcunarip 2 nil is the vernacular name bj^- which
the botanical species Gymbojmgon ccesms of Stajjf is known in
South Travancore. The grass grows wild in profusion on the dry
hill slopes, and the leaves, when rubbed, give a pleasant aroma
of ginger. Hence the name mcliippul (gingergrass). The shoots
appear early after the rains in June, and the grass flowers between
Oetober and January, when it attains a height of 6 feet or more.
It then dries up and is invariabty destroj^ed by Are. It may be
mentioned that the grass occurs in two varieties, one white and
the other red. The white variety alone was used in this investi-
gation. It has been observed that the same grass growing in
moist places or in "waterlogged tracts is almost odourless ; pre-
sumabl}^ the proportion of essential oil to w^hich the fine aroma is '
due decreases in wet lands.

The existence of an essential oil in this grass seems to have
been well known ; but the distillation of this grass for its oil,

334

PE BFU ALERT

reported to have been in practice in former years, lias now been
entirely given np. Jlcntion is made of this oil bv Parry
( Ciicinistry of Essential Oils and Artificial Perfumes,’ 1021,
vol. i.. p. G3) as having been distilled at Arni, in the ^ladras
Prcsidenc}-, but lie adds that no data arc available about the
properties of the oil.

A sample of the oil distilled from this grass in 1920 vas sub-
mitted by the Department of Industries. Travancore, for analysis
to Dr. Sudborough, of the Indian Institute of Science, Bangalore,
and also to the Imperial Institute, London. From a study of the
constants of the oil Dr. Sudborough (private report) arrived at
the conclusion that it vas not identical vith any known variot 3 ’’.
The attention of the authors was drami to this b^^ Mr. I. C. Chacko,
in charge of the Industries Department, Travancore. At his
request a more complete investigation was undertaken, particu-
larly with a view to finding out its value as a perfume oil. While
tliis paper was in manuscript, a similar report was received from
the Director of the Imperial Institute, London, who stated that
the “ inchi ” grass oil differs in its constants from all the grass
oils of commerce, and that it might be emplojmd as a substitute
for palmarosa oil, wloich it resembles in odour.

Our investigation has shown that this oil is quite different in
character from the oils jdelded by the closely allied varieties
Cyinhopo^on jlcxuosiis (Cochin lemongrass) and Cyinhopoyoii
AIoTlnii (the motia and *' sofia ” grasses of western India).
Both these oils are well known in commerce. Citral and geraniol,
the valuable constituents of the former and latter oil respectively,
are both absent in this oil ; while borneol, which has not been
reported to be present in either of them, appears to be a character-
istic constituent of the oil from ** inchi ” grass. In addition to
Z-borneoI, the oil contains Z-camphene, Z-limonene, Z-tcrpineol. and
sesquiterpene constituents which have not j'ct been identified.

Si.x hundred pounds of grass consisting of the upper third of
the plant were collected in October, 1921, and distilled in ah-dried
condition (moisture = 13 per cent.) with steam in a large copper
still over a wood fire, the still being provided with a perforated
false bottom to separate the grass from the water below, and thus
avoid overheating. The j'ield of the oil was 0-S per cent. (It may
be mentioned that this still, when used for distilling lemongras.s,
docs not compare favourably as regards yield with the so-called
coxintiy still, wliich is invariablj* eraplo 3 'ed for lemongras.s dis' illa-
tion. Therefore it is believed that the 'above 3 *icld for “ inchi ”

335

PERFUMERY

S ro

a c3 n

o w ^
u o ^

c3 <5^

O N 9 9

^ C<1 rH |> C5
^ , QO

lit

ai§

O I> T T' 9

CO o CO CO
« t-

P=H^ O

ra c^ 9 9

^ r~i KO <Z>

^ 1 o

jE2 o
00 o o >

6 S >

i> 6

CO CO

1— 1

lb o

^ 1

Cv^

O o

o o

s I

o io cb

^ 1

^ 10.

CO o o rH

• CO j> O

r-^ O

o fo
lO lO

43 ^ 43

^ ^ d

O O (D

O O O

• O O J>
-g l> CO CO

S d d d

Q .p .p .d

Ph {>3

0 ^ ^ 43

'^.^=3 a

rcS rO ^ ^

it; o o o

kHDQM 02

K ®

O CO .
^ a

a ^

• rH CJ

^ s

4> O c3

rt +3 ^
S cirri
93 -if IS
o o S

PhPh <1

■ >.c3

. C/3 O
<D H

rd ^

. «

||IJ

•d d ^

5 ^ g 'S

02<3 Ph

CD P , O

^ o

fcO CZ3
CO CP GJ

r d

^ f-H I— I

•'^ TT
rQ fd ^

rd <D O

o d) 2

CQ 4=> d

d ^ (D

-P (n r-1

P 4> <D
‘d rd

H Sh

^ d S"

_■ !**• O •/» • VVAAV,*. VJ- V XO u\j

Btanclarcl conditions ot saponilication were modilied by ns as required by the presence of terpineol.
(c) Percentage of aldehyde determined by the neutral sulphite method.

PERFUIIEIi Y

pass, considerable tliongb it is for a grass of this nature, may be
imploded bj the use of a proper still under different conditions.)
The oil, when freshly distilled from the grass, has a light crecnish-
yellow colour, which alters to light brown on keeping.'^

The constants of different samjiles of oil olffained from
different parts of the plant collected at different .stages of its
growth have been determined, and the result^ tr.bulatcrf for com-
parison. From these figures it. would appear that tlsc plant
contains a higher percentage of alcoliol in an c.U'lier stage of
grov.'tli. and that the flowers yield a larger percentage of iicavior
oil. tile higher density being due to the presence of a greater
proportion of the se.'quitorpene fraction. It is intended to
investigate further the conditions of distillation from the point
of view of quantity and quality of yield, the numlier of cuttings
which can be tal.en from the same jffant, and the best season for
distillation.

Bcfcn^imifion of AcchjJ F«?nc.— The presence of tcrpincoi in
the oil found on analysis necessitates an alteration in the usual
method of saponification. The following optimum conditions
were found for this oil : A mi.\ture of 10 c.c. of the oil, 12 c.c. of
acetic anhj'dride, and 2 grams of anh 3 *drous soebum acetate was
boiled gently on a sand bath for hours. The acetylatcd oil
was washed and dried, and about 3 grams of it saponified by
heating on a water bath for 2 hours with 15 c.c. of N/'2 alcoholic
liotash solution..

Fractionation . — ^The oil was fractionated under reduced pressure
(11 to 13 mm.), and the following fractions obtained ; —

Loilmg point.

Colour.

Pcrc^'n'ngc
by volume.

55°-90°

Colourless .

30-0

no'’-! 35°

Light 3 'cllow

3G-5

135°-1C0°

Greenish 3 'ellow .

30-0

Ke.sidue

Pitch-like .

3-5

(b 3 ’ difference)

The second fraction when cooled gave a large quanti< 3 ' of
cr\-stals possessing a camphor-IiLc odour. The e were sej.aialed
In- repeated fractionation and cooling.

Fraction 1. — This fraction was rcfractioi ated several times
under ordinary pressure, and finally about equal quantities of the

r- 337 r:

PERFUMERY

fractions A and B were obtained. As the table shows, A resembles
camphene and B resembles limonene : —

Z-Camphene.

Z-Limonene.

Boiling point .

160°-161°

159°-1G1°

175-5°-177°

175°-17G°

Refractive index

1-4540

1-4550

1-4720

1-474G

— 88-1

— 104

— 80-8

— 1C5

d—

0-8584

0-8555 at 40°

0-8490

0-8472

A was definitely identified to be Z-campliene by preparing its
liydi’ochloride, and also by converting it into isoborneol in the
usual way. An attempt to obtain the sohd h 3 ^drocarbon succeeded
only partially. An attempt was made to prepare a solid hydro-
ehloride from B, but it did not succeed. A tetrabromide was,
however, obtained and identified as Z-limonene tetrabromide. -

Fraction 2. Identification of the Solid. — It was ciystallised
several times from petrol and found to melt at 203° to 204°.
It was identified as borneol by the melting point, boiling point,
specific rotation, the chloral compound, its p-nitrobenzoatc and
acid phthalato. Borneol has not been reported to be present in
any of the similar Cymbopogon oils, and therefore it would seem
that the essential oil from Gymhopogon ccesius may be charac-
terised by the presence of tliis alcohol.

Identification of the Liquid. — The liquid obtained after the
removal of borneol was redistilled under atmospheric pressure
with an eight-pear fractionating column, and about 8 per cent,
jdeld (calculated on the original oil) of a colourless sweet-smelling
oil possessing the following constants was obtained : —

Boiling point

n,30°

[«].30°

Oil.

216°-219°

Torpineol.

217°-218°

0- 9380 .. 0-933-0-941

1- 4830 . . 1-4800-1-4840

— 56-4° . . +100

The oil was suspected to consist of Z-terpineol. This was
confirmed by the preparation of dipentene dihydriodide from it
b^haking with hydriodic acid.

'^INDOL. — This is a substance of considerable value to the
perfumer. Closely related to it is the body scatol, and an isomeric
meth 3 d-indol, which will be conveniently discussed together with

338

PERFU M Eli Y

inclol. Althougli thc^c bodies have very offensive odours in the
concentrated form, when they are highly diluted they greatly
improve floral odom'S to which thc\' are adaptable. It is of interest
to note that the essential oil of jasmin, when extracted direct
from the flowers, contains no indol and no methyl anthranilatc.
But if the flowers arc allowed to macerate in cold fat, so that the
life processes arc allowed to continue in the tissues, more oil is
developed in the flowens, as the original supph’ passes into the
fat. In this further supply of essential oil, both indol and methyl
anthranilatc appear, so that it is probable that these bodies pre-
existed in the form of glucosidcs, which arc broken down in the
further biological changes in the plant. The result is that the
jasmine jjerfume obtained by enfleurage is vastly superior in odour
to that obtained bj’ e.xtraction with a volatile solvent. It is
strange that a substance so objectionable in its natural condition
should be of such great value as a perfume material when diluted.
It has been discovered in foeccs by Briegor {Jour. Prakl. Chom.,
2, 17, 133), and in the ordinary digestive products by Nencki and
Kiihne. It is present in enfleurage oil of jasmine, in neroli oil,
clove flower oil, and the oils of CeJlis reliculosa, Rohinia pseud-
acacia, Calladium, Miirraya exoiica, and Visnea viocancra. It
has also been found in the vapours given off in the extraction of
sugar from molasses. In this case it is accompanied by scatol.

Indol CsH-N is the mother substance of the indigo group of
compounds, and was discovered by Bayer in 1SG6 {Annahn,
140, 4). Although Lipp was actualh’- the first to s3'nthesisc indol,
bj’ the condensation of sodium ethjdate with amino-chlor-
styrpleno {Berichie, 1SS4, 17, 10G7), the practical development of
the chemistry of indol is due almost entueh' to Ba 3 ’er. Indol is a
ciystalline bod 3 ’ melting at 52° and boiling at 244°. It should onl 3 ’
be used in minute quantities in floral combinations, as, if used in
e.xcess, not onl 3 '' is the perfume ruined, but the indol tends to
darken in colour, which under certain circumstances is ver 3 '
objectionable.

Scivtol is /J-mctlnd-indol, CsITc,N(CHj), and i.s found in ordinary
civet and' in the e.ssential oil from tlie wood of Celiis reliculosa.
It forms white cr 3 ’.slals, melting at 95°, and boiling at 205° to
2GG°. It viclds a Imlrochloride melting at 1G7° to 1GS°, of the
formula [CsII(;X(Cir 3 )].JICl, and a picric acid com})Ound melting
at 172° to 173°. It is cqualh' foul-smelling witii indol, aTid
nia 3 ' bo used in the same manner, but with even greater
caution.

339

PERFUMERY

There is an isomeric metli 5 ’’l-indol, Icnorni as methyl-indol-2 or
metli 3 d-ketol C 8 HglS[(CIl 3 ). This has been prepared by Tischer by
delwdrating the phenyl-hydrazone of acetone b}'- means of "zinc
chloride at 180°. The reaction is accompanied bj'' the evolution
of ammonia. It is a crystalline body melting at 69°, and boiling
at 268°, and similar to scatol in its general properties.

Scatol is artificially prepared in a manner similar to that used
for the preparation of its isomer. The phenjd-hydi’azone of
propanal CgHg.NH.N ; CH.CH 2 .CH 3 is dehydrated, preferabty by
means of cuprous chloride. Arbussow and Tichvinskj'’ {Berichte,
1910) obtained a yield of 60 per cent, of the theoretical in this
manner. Scatol may be identified by its forming a fine blue
colour with a solution of dimeth 3 d-amino-benzaldeh 3 ’’de. There
are numerous methods by which indol can be prepared artificiall 3 ^
Most of these, however, are of purel 3 ’' theoretical interest, and onty
those of some practical importance will be referred to here. To
obtain indol naturall 3 >', the following process ma 3 ’’ be used. The
essential oil containing it is mixed with 10 per cent, of picric acid
and heated to 60°. An excess of petroleum ether is then added.
A picric acid compound of indol separates out in long red cr 3 ’-stals,
which are washed vdth petroleum ether and decomposed by
caustic alkali, the indol thus liberated being dissolved out by
extraction with ether, and the residue left on evaporation of the
ether is steam distilled, when pure mdol passes over. This method
is adapted for a fairly accurate quantitative determination.
To prepare indol on a satisfactor 3 '’ scale, the following processes
may be emplo 3 ''ed. It is prepared by the reduction of ortho-
nitro -cinnamic acid by means of zinc dust. It is prepared to a
considerable extent as a secondary product during the synthetic
manufacture of indigo. If anthranilic acid be treated with mono-
chloracetic acid, phenyl-glycin-or//m-carbonic acid results. B 3 ''
the careful heatmg of the lime salt of this acid, indoxyl CgH^NO
results, which b 3 ’' reduction 3 delds indol. Or antliranihc acid is
condensed with hydrocyanic acid and formaldeh 3 J'de. This results
in a nitrile CcH 4 (]SrH.CH 2 CN)COOH, which on saponification
yields the free acid C(,H 4 (NH.CH 2 .COOH)COOH, phen 3 d-glycin-
ori/io-carhonic acid, which is treated as above described.

Other processes which have been recommended for the pre-
paration of indol are those of Berlinerblau (Monatshefic, S, 187) ;
Thiele and Dimiroth {Berichte, 1895, 13, 1411) ; Vorlander-Apelt
{Berichte, 1904, 1, 1134) ; Glaud {Jour. Cheiji. 80 c,, 1913, 103,
1254), and Weermann (German patent 139822).

340

PERFUMDRY

In addition to the colour reaction mentioned above for scatol,
the following colour reactions for indol and scatol may be noted.
If a few drops of dimethyl-anilme be added to 6 c.c. of a cliloro-
formic solution containing indol, and a little concentrated sul-
phuric acid be cautiously added, a pale red colour appears at the
junction of the liquids, insoluble in chloroform, in the presence of
indol ; or a violet coloration, soluble in chloroform, in the case of
scatol. IVith citral instead of dimethyl-aniline, there is a j^ellow
coloration with indol, and a red coloration with scatol. These
reactions are sensitive to from 1 in 200,000 to 1 in 500,000. T’inalljq
if a few drops of an alcohohe solution of vanillin (5 per cent,
strength) are added to a dilute solution of indol or scatol, and the
mixture be heated with a slight excess of concentrated hydro-
chloric acid, an orange -brown colour results in the presence of
indol, or a violet colour in the presence of scatol. The useful
table of indol derivatives on p, 341 is due to IMirgodin (in La
Parfumene Moderno).

INULA OIL. — The essential oil of Inula viscosa is a pale
brown hquid of powerful aromatic odour, recalling hyssop and
eucatyptus. It has the following characters : —

Specific gravity .... 0*9436

Optical rotation . . _ 24°

Scldmmel & Oo. {Report, October, 1903) have reported on an
oil said to be obtained from this plant, but which had characters
differing from the above.

Tliis oil had the following characters : —

Specific gravity at 25° . . 1*006

Acid value . . . . .164*6

Ester value . . . . .15*8

The plant is widely distributed in Algeria, and is found in the
Alpes-Maritimes, and is very abundant in the uncultivated lands
of the Maures and the Esterel. The allied plant, Imila graveohns,
has an odour of lemons. Its characters are as follows : —

Specific gravity .... 0*9754

Oifiical rotation . . . . — 36° 40'

Refractive index .... 1*4759

Acid value . 8*45

Ester value , . . . .161*3

Ester value after acetylation . . 239*4

It probably contains bornyl acetate. Inula Eelenium is
Elecampane,

342

PEBFV M EH Y

lONONE. — ^Tho discoven,* of the original artificial violet per-
fume i.-^ one of the outstanding triumphs of modern chemical
research. This bod}’ vas named ionone by its discoverer, and
although to-day there are variotis allied derivatives, it will be
convenient to deal with the whole of the artificial violet compounds
under this title.

The -perfume of the violet is one of the most popular of the
floral odours, but since the actual percentage of odoriferous
material is so minute, it has never been possible to isolate sufficient
of the cssejitial oil for a proper investigation to be made. So
expensive would such an investigation be that Tiemann and
Kriiger, recognising the similarity between the odours of the
violet and of orris root (it will be remembered that the old-
fashioned “ Ariolet powder ” never contained violet perfume, but
was merely powdered" orris root mixed with starchy matter),
decided to carry out an investigation on the odorous substances
of orris root in the hopes that the results would lead them to the
knowledge of the violet perfume. Whether this has actually been
the case no one knows, but the results of their work and its further
development b 3 ’’ others have been so successful that the artificial
violet perfumes available in consequence are accepted as satis-
factory’", and it is unlikely that the difficulties attending an
exhaustive research on the actual violet perfume will be overcome
for many' years.

Tiemann and Kriiger, whose results were first published in 1893
{Berichic, 1893, 26, 2675), worked on orris root, which was
extracted with ether, the ether recovered, and the residue steam
distilled in order to ehminate the fixed fatty’- matter, which con-
sists of resins, irigenin, iridic and myristic acids, etc., whilst the
volatile portions consist of a little my'ristic acid and its methyl
ester, oleic acid, oleic anhydride, and the characteristic odour
bearer, which the discoverers termed irone. It was found that
this body was a ketone of the formula CijHooO. It is an oil which,
in the concentrated form, docs not resemble violets, but which,
on dilution, has a marked resemblance to the violet iicrfume.
Although it is a ketone, it cannot be succes.sfully' purified by
means of a bisulphite compound. Such methods as using its
hydrazone as an intermediary have to be resorted to. Having by
a prolonged study of irone and its decomposition products ascer-
tained its constitution, Tiemann and Kriiger set out to synthesise
it. As a result of these experiments, isomers of irone were obtained ,
which wore at first believed to be but a single body, to which the

343

PEEFUMER Y

name ionone was given. The resolution of this into its isomers
followed at a later stage. In the meantime the powerful violet
odour of ionone was such as to render it unnecessary, at all events
from a commercial point of view, to follow up the h'one research,
and for the time being the synthesis of h’one was not achieved.
This, however, has since been achieved, and an interesting paper
on the subject was pubhshed by Merling and Welde {Aniialen,
1909, 119) upon the question. Two parts of ethyl acetoacetate
and 1 part of acetone arc condensed at — 5° with the aid of
hydi’ochloric acid. This results in isopropylidene aceto-acetic
ester (0113)20 : 0(000H3).002.02H5. Tliis ester is then con-
densed with the sodium compound of ethyl aceto-acetate (German
Patent 14S0S0 of 1902). The chain is thus closed, and the ethyl
ester of trimethyl-cyclohexane-carboxyhc acid results. To 100
parts of this ester 100 parts of phosphorus pentachloride are
added, the temperature being kept very low. The body is thus
transformed into the corresponding ester of dichlorcj^clogeranic
acid, which, by loss of hydrochloric acid, is changed into the ester
of the monochlor acid, and this, on reduction by sodium, becomes
saturated by talcmg up 4 atoms of hj^drogen, and from tliis fully
saturated compound 1 molecule of hydi’ogen chloride is abstracted,
leaving ethjd- A -4-cyclogeranate .

This ester is decomposed mto the free acid, which exists in two
stereoisomeric forms, and which, by Merling’s process, are con-
verted into the correspondhig aldehj^de. (For details of tliis
transformation, see La technique industrielle des jiarfums
synthetiques ” (Paris, 1923, R. Sornet), pp. 86-87.) Irone results
when the aldehyde so prepared, A-4-cyclocitral, is condensed with
aeetone. Irene exists in two stereoisomeric forms, a-irone and
/5-h’one. The mixed body “ irone ” has a powerful violet odom’,
and has the following characters : —

Boiling point at 16 mm. . . . 144°

Specific gravity .... 0*940

Refractive index .... 1*6011

Optical rotation .... about + 40°

Coming back to the initial results of Tiemann, it was found that
the substance resulting from the condensation of citral and acetone
in the presence of an aUcah was not irone, but an isomer having a
powerful violet odour (on dilution), which resulted from the
following reaction : —

CioHxcO + (CH 3 ) 2 C 0 = C13H20O -f H2O.

Citral Aeetone

344

PERFU MEJR Y

As a result of further researches, this body, udheh veas of a
ketonic nature, u-as named pseudoionono. It was found that, if
this body ■were lieated with dilute sulphuric acid and a little
glycerine, it was converted into another isomer, to wliich the
name ionone was given. This substance is the original iononc of
commerce, which was sold at a fabulous price in a 10 per cent,
solution in alcohol. It is now recognised to be a mixture of two
isomeric ketones. The complete patent specification for this
body, which ma}' be described as epoch making in the art of
perfumery, is of sufficient importance to be reproduced tcxtually.
It reads as follows : —

“ I, J. C. W. F. Tiemann, member of the firm of Haarmann
and Reimer, of Holzrainden, residing at Berlin, Germany, do
hereby declare the natm’e of this invention, and in what
manner the same is to be performed, to bo particularly described
and ascertained in and by the following statement : I have
found that a mixture of citral and acetone, if it is subjected
in the presence of water for a sufficiently long time to the
action of hydrates of allraline earths, or of hydrates of alkali
metals, or of other alkaline agents, is condensed to a ketone
of the formula C13H00O. This substance, which I term ‘ pseudo-
iononc,’ may be produced, for instance, in shaking together for
several days equal parts of citral and acetone with a solution
of hydrate of barium, and in dissolving the product of this
reaction in ether. The residue of the ether solution is frac-
tionally distilled under a reduced pressure and the fraction is
collected, which boils at a pressure of 12 mm. at a temperature
of from 138° to 155° C., and from it the unaltered citral and
unchanged acetone and volatile products of condensation of
acetone by itself are separated in a current of steam, which
readily carries oil these bodies. The product of condensation
remaining in the distilling apparatus is purified b}' fractional
distillation in vacuo. Under a pressure of 12 mm. a liquid
distils off at a temperature of from 143° to 145° C. This
product of condensation of citral with acetone, which I terra
pseudoionone, is a ketone readilj’^ decomposable by the action '
of alkalies. Its formula is Cj^HogO ; its index of refraction,
Rej = 1"527 ; and its specific weight, 0-904. The pseudoionono
has a peculiar, but not very .pronounced, odour; it docs not
combine with bisulphite of sodium ns most of the ketones
of the higher series, but in other rc.spccts it possesses the
ordinary characteristic properties of the ketones, forming, in

345

PERFUMERY

particular, products of condensation with plienylhydrazine,
hydroxylamine, and other substituted ammonias. Although
the odour of the pseudoionone does not appear to render it
of great importance for its direct use in perfumery, it is
capable of serving as raw material for the production 'of
perfumes, the pseudoionone being eonvefted by the action of
dilute acids into an isomeric ketone, which I term ionone, and
which has most valuable properties for perfumery purposes.
Tliis eonversion may be effected, for example, by heating for
several hours in an oil bath 20 parts of pseudoionone with
100 parts of water, 2-5 parts of sulphuric acid, and 100 parts of
glycerine to the boiling point of the mixture. The product
resulting from this reaction is dissolved in ether ; the latter is
evaporated and the residue subjected to fractional distillation
in vacuo. The fraction distilling under a pressure of 12 mm.
at a temperatm’e of from 125° to 135° C. is eollected. This
product may be still further purified by eonverting it, by means
of phenylliydrazine or other substituted ammonias, into a ketone
condensation product decomposable under the action of dilute
acids. The ketone derivatives of the pseudoionone are converted,
under similar eonditions, into ketone derivatives of the ionone.
The pure ionone corresponds to the formula CigHgoO, it boils
under a pressure of 12 mm. at a temperature of about 128° C.,
its specifie weight is 0-935, and its index of refraction is = 1-507.
The ionone has a fresh flower perfume recalling that of violets and
vines, and is pecuharly suitable for being used in perfumery,
confectionery, and distillery. The ionone, when subjected to a
temperature surpassing 100° C. to the action of hydriodic acid,
splits off water and gives a hydrocarbon corresponding with the
formula CigHjg, boiling under a pressure of 12 mm. at a tempera-
ture from 106° to 112° C. This hydrocarbon is converted by
strong oxidising agents into an acid of the formula CjoHigOg,
melting at a temperature of 214° C.”

Many patents for the production of artificial violet perfume
have been taken out since the original patent, but the most
important detail in the chemistry of ionone since then is the dis-
covery that commercial ionone is actually a mixture of two
isomeric bodies, which have been termed a-ionone and /9-ionone.

Pseudoionone has the following characters : —

Specific gravity at 20° . . . 0-898

Refractive index at 20° . . . 1-53346

Boiling point at 12 mm. . . . 143°-145°

346

PEJiFlJ MEB r

CoPuTucrcial 100 per cent, ionone has, approximately, the
following characters : —

33'iiiing point at 10 nim. . . . 12G'-12S°

Specific gravity at 15° . . . 0'035-0'940'

Ilefractivc index at 20° . . . 1-5035-1-5070

Optical rotation . . . .0°

The characteristic odour of this pure (mixed) ionone is that of
violets, with a suggC'tion of the odour of vine leaves and blossoms.
Ticinann {Bcrichte, ISOS, 31, SOS, SG7) .succeeded in resolving this
substance into a-ionone and ^-ionone. Bj' heating pscudo-
ionone with dilute sulphuric acid, a diilercnt product is obtained
from that ;ricldcd when strong sidiJhuric acid is used. In the
latter case, /?-ionone predominates. a-Ionone is prepared from
the commercial product by converting it into the crystalline
oxime, which is reciystallised from petroleum ether, when the
ketone can be regenerated by the action of dilute sulphuric acid,
when a-ionone results. This isomer has the following characters : —

Specific gravity at 15° . . . 0'934

Refractive index at 20° . . . 1*4990

Boiling jDoint at 12 mm. . . . 127°-128°

Jlclting point of oxime . . . 89°-90°

Melting point of scmicarbazone . 107°

Slelting point of bromphenylhydrazone 142°-143°

/9-ionone is obtained from the commercial product by means of
the scmicarbazone, which crj'stalliscs more readilj’' than the
corre.sponding derivative of a-ionono, and can thus be separated,
^-ionone has the following characters : —

Specific gravity at 15° . . . 0*949

Boiling point at 12 mm. . . . 134°— 135°

Refractive index at 20° . . . 1*5198

Molting point of scmicarbazone . 148°— 149°

Zilelting point of bromphcnjdhydrazone 11G°-118°

Lewinsohn (P. cC* E. 0. B., 1923, 259) gives the following account
of the modem technical method for the manufacture, of ionone ; —

Contrarj' to the descriptions in the patents and sundry publi-
cations, the technical preparation of ionone is as follows : The
process involves two stages : (a) the condensation of lemongrass
oil with acetone to form pseudoiononc ; (h) the ring-closure or
cyclisation of pseudoiononc with production of a- and /?-iononc3.
The German patent (D.R.P. 75120) taken out by Jlcssrs. Haar-
mann and Reimcr of Hoizminden for the preparation of ionone
claims the condensation of citral with acetone. The modern

S17

PEB.FU MERY

practice is to use, in place of citral, the lemongrass oil from which
citral is obtained. This makes the process cheaper, and in no
way affects the final product.

{a) ConclGnsaiion . — mixture of equal parts of lemongrass
oil, acetone, and 10 per cent, caustic soda solution is stirred for
seventy-two hours in an iron stirring vessel, the temi^erature not
being allowed to exceed 35°. (In subsequent batches recovered
acetone ma}^ be used, but the caustic liquor must be more con-
centrated to allow for the v'ater contained in the acetone.) At the
end of this time the lower aqueous layer is removed, and the
upper laj^er is washed several times vuth water. From the
aqueous laj^er and washings acetone is recovered by distillation.
The reddish brown oity layer is then distilled in vacuo. Methyl-
heptenone (formed from the citral) comes over first, and the
pseudoionone is collected at 135° to 150° at 5 mm. The yield is
almost quantitative, allowing for the fact that lemongrass oil
contains only 70 per cent, of citral, a portion of which, as men-
tioned above, is converted into methylheptenone.

(6) CycUsaiion . — The cyclisation of pseudoionone requii’es the
greatest care and skill on the part of the operators. According
to the concentration of the sulphuric acid used and the tem-
perature of the reaction, varying mixtures of a- and /5-ionones are
obtained. Since the former is esteemed more highty and is more
valuable than the ^ compound, the manufacturer must aim at
producing the greatest proportion of a-ionone. The use of an
unsuitable dilution of sulphuric acid results in much unchanged
pseudoionone and little a-ionone, the main product being /5-ionone.
On the other hand, if the concentration of the acid be too high
there is formed, together vdth relatively large amounts of a-ionone,
much resmous residue, and no pseudoionone is recovered. For
a maximum yield of a-ionone, therefore, the strength of the acid
must not be increased unduly. The process here described gives'
a product containing about 90 per cent, of a- and 10 per cent, of
/S-ionone.

One part of pseudoionone prepared as above and 3 parts of
60 per cent, sulphuric acid are separately cooled to — 8° with
continuous stirring. The acid is then allowed to run into the
pseudoionone. A rise in temperature is observed. As soon as
the thermometer reaches 30° there is seen a sudden change in the
dark brown colour, which for some moments becomes clearer.
The mixture is now heated as rapidly as possible to 42°, and at
once poured upon finely powdered ice. When the ice has melted

348

PEBFU MEB r

tlie crude iononc floats on the surface as a bro'vvn oil. The acid
laj-er is removed, and extracted vitli benzene. The extract and
the crude ionone are united and together washed uith water,
then with dilute sodium carbonate solution, and finally again
vdth water. The crude product so obtained is distilled in vacuo,
the water and terpene b.y-products being removed at 10 to 12 mm.,
and the iononc itself distiUod in a good machine-vacuum at not
more than 2 to S mm. pressm-e. At this pressure a-ionone
boils at 11S° to 125°, /S-ionone at lvS0° to 135°. With good
working there should be no unchanged pscudoiononc. When the
temperature reaches 135° the distillation is discontinued, and the
falling of the mereuxy in the gauge is the signal for the empt 3 dng
of the distillation vessel, since the residue quickl}' sets. With
well-tramed worlcers the jdeld of distilled ionones is about 40 per
cent, of the weight of Icmongrass oil used, or 70 per cent, on the
citral content. The further purification of the ionone so produced
(wliich is itself a commercial article) to give such brands as
“ ionone extra ” and “ ionone blanc ” necessitates other, some-
what delicate, treatments.

The ionone manufacturer who follows strictly the process
described above can be sure of alwaj's obtaining a constant
product, which, enhanced bj’- the addition of a few drops
of “violet green scent” (or, to give it its chemical name,
methjd-heptine-carbonate), will find regular purchasers amongst
perfumers.

Prom the above, it is easily miderstood that pm’e 100 per cent,
ionone maj'- varj’- considerabl 3 - according to the exact method of
manufacture, and perfumers must judge ionone on its odour,
quite apart from its purity. One perfumer ma 3 ’- prefer an ionone
with less, wliilst another prefers more, /9-ionone in the product.

It is, moreover, possible to separate the two isomers on a
commercial scale. (See especiall 3 ’- Tiemami, French Patent
No. 229G83 ; and Chuit and Bachofen, Bev. Chim. ptir. el applique,
1903.)

The hydrosulphonic compound of a-ionone cr 3 ’'stallises more
readily than the corresponding compound of /?'ionone, wliilst the
latter is the more easily decomposed b 3 ’’ a current of steam.

Chuit and Bachofen base their method of separation on the
relative insolubility of the sodium salt of the hydrosulphonic
compound of a-ionbne in the presence of sodium chloride, whilst
the corresponding /5-compound remains in solution. If sodium
chloride be added to a hot solution of the h 3 '’drosulphonic com-

349

PERFUMER Y

pounds, separation of the a-salt takes place slowly as the solution
cools, and the salt crystallises in fine white scales, which can he
recrystallised from hot water. The /5-compound remains in
solution. From the perfumer’s point of view, the complete
separation of these isomers enables one to produce numerous
shades of violet perfume, since a-ionone has the sweeter and more
penetrating odour, whilst /5-ionone, although not so sweet,
resembles the true violet flower more completely.

By reducing ionone Skita {Bericlitc, 1912, 45, 3312) has pre-
pared the corresponding dihydroionones, wliich have odours
recalling that of cedarwood. Tiemann, however, has prepared a
dihydroionone apparently isomeric mth the products of Skita by
the condensation of oitronellal and acetone. The method is,
generally, identical with that employed in the condensation of
citral and acetone. Diliydroionone thus produced has a sweet
odour of fresh flowers.

A somewhat different shade of odom’ is produced by the use
of homologues of citral for the condensation. Thus, by using
methyl-ethyl-ketone — which is a much more difficult and tedious
condensation than when acetone is used— a methyl-pseudoionone
results which boils at 160° to 176° at about 20 mm. pressure.
By cyclisation as in the case of pseudoionone, it yields methyl-'
ionone boiling at 155° to 160° at 24 mm. pressure. Methyl-ionone
has an odour somewhat different from that of ionone, and generally
regarded as superior to the latter. Bm’and, Huguenin, and
Barbier (French Patent 278338 of September, 1898) have con- •
densed mesityl oxide, CH3.CO.CH : C(CH3)(CH3), vdth citral at
the ordinary temperature for fifteen hours, with continual agita-
tion, in the presence of caustic soda. This results in the formation
of pseudoianthone, CicHg^O, a liquid boiling at 180° to 185° at
10 mm. pressure. By cyclisation by means of 65 per cent, sulphuric
acid in the cold for half an hour, ianthone results. This is a
highly odorous liquid boiling at 161° at 10 mm. pressure, having
a violet odour which differs distinctly from that of ionone.

A body known as cyclo-geraniolidene-acetone has been prepared
which is, again, another synthetic violet with a characteristic
shade of odour of its own {Rev. GJiem. Ind., 1904, 141). If sodium
and carbon dioxide be allowed to act on trimethyl-cyclo-hexanone,
the corresponding carbonic acid is produced. By the action of
reducing agents, tliis is transformed into trimethyl-oxy-cyelo-
hexanone-carbonic acid. If the calcium salt of this acid is dis-
tilled with calcium formate, cyclo-geraniolidene-aldehyde, CioHjeO.

350

PERFVMEEl

results. B}’- condensation •nith acetone, tliis yields cj’-clo-goranioli-
dene-acelone, wliicli is a mixture of two isomers. In practice, this
interesting and valuable violet perfume is prepared as follows.
Pure ether (4,500 parts) is mixed with sodium (98 parts), and
trimcthjd-cyclo-hexanone (450 parts) added. The mixtme is
kept under a reflux condenser, and when the sodium is dissolved
a current of COo is passed through the liquid, which is kept cool,
to saturation. A gelatinous mass results, which eventually
crystallises. This is poured on to ice. The ether retains unaltered
trimethyl-C3''clo-hexanone, whilst bj’’ the addition of a dilute acid
to the aqueous solution, trimethyl-cj'clo-hexanonc-carbonic acid
is precipitated. To 100 parts of the sodium salt of this acid
4,000 parts of sodium amalgam (2 per cent.) are added, the solution
being dilute and kept cold, A current of COo is passed through
the liquid. When reaction is complete, dilute sulphuric acid is
added, and trimcthyl-oxy-c 5 '’clo-hcxanone-carboruc acid is precipi-
tated. The calcium salts of this acid and of formic acid are then
distilled in equimolecular quantities in a current of h 3 ’’drogen.
The resulting cj'-clo-geraniobdene-aldehj’-de is rectified in vacuo,
and 15 parts of the pure compound (which is a mixture of two
isomers) ai'c dissolved in 50 parts of acetone, and 0*75 part of
sodium in 15 parts of absolute alcohol are added, the mixture
being kept upon ice. The mixture is then neutralised. The a
and (i ketones thus formed are separated by fractional distillation.

IMaschmeyer (French Patent 354050 of 1905) has prepared
methj’l-cj’clo-citrjdidene-methoxy acetate by the condensation of
citral with methjd chloracctate. The product has a strong violet
odour.

Verlej’- (English Patent 14613, 1897) has prepared a seiies of
compounds having a %doIet odonr depending on the reaction of an
acid chloride on C 3 ’’mene in the presence of aluminium chloride.
Tliis results, for example, in the formation of propion 3 d-c 3 ’myl
ketone. The ketone is brominated, and the bromo derivative is
treated with sodium acetate, the acetic ether so obtained having
an odour of orris root, or violet.

Hanriot communicated to the Eighth Congress of Applied
Chemistry (New York, 1912) a characteristic colour reaction for
the detection of ionone. The ionone is dissolved in concentrated
hydrocliloric acid. An intense golden yellow coloration is pro-
duced. If chloral h 3 ^di'ate be added and the liquid be heated, it
-turns a dirty violet colour. The liquid is allowed to cool and is
shaken with ether. It is thus decolorised.

351

PERFU MERY

The ethereal solution, when evaporated in the cold on a watch
glass, deposits a distinct violet colouring matter, soluble in water,
instantaneously decolorised by ether. This last reaction is so
delicate that it is sufficient to pour the vapours of ether on to the
watch glass to produce the dccolorisation of the violet'substance.

Iso-ionone gives the same reaction. It is even probable that
this reaction only occurs ^vith ionone after its conversion into
isoionone by the hydrochloric acid. As a matter of fact, it has
not been possible to obtain the reaction in a neutral or alkaline
medium.

Neither pseudoionone, nor oil of orris root, nor the natural oO
of violets gives the reaction, which is sensitive with ionone in
proportions of 1 in 2,000. It is thus possible to detect the presence
of ionone in a large number of commercial perfumes.

The presence of the natural essential oils does not appear to
interfere vdth the reaction.

IRALDEINE. — ^This name is that of one of the artificial violet
perfumes. It is usuallj’ methylionone. (See “ Ionone.”)

IRIS FLORENTINA.— See “ Orris Root.”

IRONE.— See “ Ionone.”

ISOAMYL ALCOHOL. — ^This alcohol, of the formula
(CH 3 ) 2 .CH(CH 2 ) 20 H, is found in the various eucalyptus oils, and
also in geranium, lavender, and peppermint oils. It also occurs
in the form of esters in the oils of Eucalyptus globulus, EucalypUis
aggregata, and in Roman camomile and cognac oils. It is an
odorous liquid boiling at 131°, and yields a phenylurethane
melting at 61° to 62°.

ISOANETHOL.— See “ Estragol.”

ISOBORNEOL. — Isoborneol is a stereoisomer of borneol,
CioHi,OH ig.v.). It closety resembles borneol in general charac-
ters. It results, together with borneol, on the reduction of the
ketone, camphor, by means of sodium, or it may be prepared by
causing the terpene camphene to take up water under the action
of acetic and sulphiu'ic acids. It ma}?- be prepared in the follo^ving
manner. One hundred grams of camphene are heated, with
260 grams of glacial acetic acid and 10 grams of 60 per cent,
sulphuric acid, to 60° for four hours, the mixture being continually
shaken. When the reaction is complete, a large amount of water
is added, when isobornyl acetate (formed by hydration of the
terpene, accompanied by a molecular rearrangement, and acetyla-
tion of the so formed isoborneol) results. Excess of free acid is

352

PERFUMERY

waslierl nway witli fl-ater, and the separated ester is saponified in
the usual manner bj'- saponification under a reflux condenser.
Tlie^ greater part of the alcohol is distilled off, and the residual
liquid is poured into a large volume of water. The isoborneol is-
precipitated, collected on a filter, washed with water, dried on a
porous plate, and finally rccrj'stallised from petroleum ether.
The melting point of isoborneol is usually given as 212°, but
according to Henderson and Heilbron {Proc. Chcm. Soo., 1913, 29,
381) it is 217°. Its' specific rotation is + 34°. On oxidation
isoborneol ^fields camphor. It forms a phen}’! -urethane melting
at 138° to 139°. It can be easily differentiated from borneol by
the fact that, on heating a solution of isoborneol in benzene for
an hour "ndth zinc chloride, camphene is obtained. Pure borneol
under identical conditions remains practically unchanged.

ISOBORNYL ACETATE.— This ester, CjoHiyOoC.CHg, re-
sembles bornyl acetate in its sharp fragrant odour. It is an oil -
of specific gravity 0-9905, and boils at 107° at 13 mm.

ISOBORNYL FORMATE.— Tliis ester, CioHj-OaC.H, is a
fragrant oil of specific gravity 1-017 ; it boils at 100° at 14 mm.
pressure.

ISOBUTYL ACETATE. — This ester, (CH 3 ) 2 CH.CH 2 .
COOCH3, '^'hicli has a fruity odour, has a specific gravity about
0-875, refractive index 1-3920, and boils between 110° and 120°.
The commercial article is probably a mixture of isomers.

ISOBUTYL ALCOHOL. — ^This alcohol, of the formula
(CH3)2CH.CH20H, is found in the distillation waters of Eucalypixis
(tinygclalinci. It boils at 108° to 109°, and has a specific gravity
0-8025. Its phenyl-m-ethane melts at 80°. It forms a number
of highly aromatic esters which are useful in perfumery.

ISOBUTYL BENZOATE. — This ester, (CH 3 ) 2 CH.CH 2 .
COO.CgHg, is an oil of very sweet odour, and is often sold as

EgHntine 100 per cent.” It is used in the manufacture of
sweet pea perfume. It is an oil of specific gravity 1-006, and
refractive index 1-4942. It boils at 237° to 238°.

ISOBUTYL BUTYRATE. — ^This ester has a very fruity
odour, and as met with in commerce is a mixture of isomers. It
has a specific gravity about O’SGo, and boils between 152® and 15S®.

ISO BUTYL FORMATE. — ^This ester, which resem’ Ics the
acetate, is an oil of specific gravity about 0-890, and boils at 98°
to 100°. -

PERFUMERY

ISOBUTYL PHENYLAGETATE.— This ester, which some-
times enters into the composition of perfumes known as ” Ideal ”
and “ Eglantine,” is usually a mixture of isomers. It has a
specific gravity about 0’990, refractive index I'lSGO, and boils
at 254°.

ISOBUTYL PROPIONATE.— This ester resembles the
acetate, and has a fruity odour. It has a specific gravity about
0-896, and boils at 137° to 138°.

ISOBUTYL SALICYLATE.— This ester resembles amyl
salicylate in odour, and is very useful in the preparation of
artificial orchid perfumes and in such compositions as irefle.
It has the formula (CH 3 ) 2 CII.CIl 2 COO.CgH 4 (OII). Its specific
gravitj'" is about 1-075 ; refractive index, 1-5100 ; and boiling
point, 259° to 260°.

ISOBUTYL VALERIANATE. — ^This ester has a very fruity
odom’. The commercial article is a mixture of isomers having
the following characters : specific gravitj'- about 0-858 to 0-862 ;
refractive index, 1-4057 ; and boils from 164° to 170°.

ISOCARYOPHYLLENE. — ^The scsquitcri^ene mixture iso-
lated from oil of cloves on the extraction of the eugenol therefrom
is, in reality, a mixtm’e of two, if not thi-ee, sesquiterpenes.
Similar mixtures exist in various other essential oils, such as
pepper, cinnamon, and copaiba oils. {Vide “ Caryophyllene.”)
Deussen and Lewinsohn {Annalen, 356, 1 ; 359, 245) first showed
that this was the fact. They separated the clove oil sesquiterpenes
into two main fractions having the follovnig characters : —

Boiling point at 16 mm. . 132°-134°

Specific gravity at 20° . 0-903

Specific rotation . . — 4-67°

Refractive index . . 1-4097

128°-128-5°

0- 910
— 23-57°

1- 4990

Of these. No. 1 was probably optically inactive, but con-
taminated with a small amount of optically active sesquiterpene.
To tliis Deussen gave the name a-car 3 '-ophyllene, and to the
optically active bod}^ the name |ff-caryoph 3 ^IIene. A thu’d isomer
was separated, boiling at 124° to 125° at 14 mm., and having a
specific rotation — 22-22°. This body appears to be identical
with what'w-as then known as isocaryophyllene, and to it Deussen
gave the name y-caiyophyllene. Semmler and Mayer {Rerichte,
44, 3657) agree generally wdth Deussen, but have much comph-
cated the whole matter by introducing a fresh and emphical

364

PEEFUMBB Y

nomenclature. The}' agree nith Deussen that crude caryoph3dIene
consists of three distinct individuals. They maintain that
Deusscn’s a-caryophyllene is identical with Chapman’s humulene,
isolated from oil of hops (\Tithout, m the writer's opinion, sufficient
experimental evidence). The two other isomers they suggest
naming fcj'p-caryophyllene, on account of some relationship the}'’
thmk exists with terpinolene, and h‘j?i-caryophyllene, on account
of a similar relationship with limonene. (For further details of
this very complicated subject, reference may be made to E. J.
Parry, “ The Chemistry of Essential Ohs, etc.,” 4th ed., vol. ii.,
pp. S4r-88.) From the perfumer’s point of view, caryophyllene
may be regarded as the main constituent of the Light oil of cloves
obtained on extraction of the eugenol, and which is very useful
in cheap soap perfumery where a clove or carnation perfume is
desired.

ISOESTRAGOL.— See “ Anethol.”

ISOEUGENOL. — ^Isoeugenol, OioHigOa, is a phenol which is
found to a very small extent hi nature, but which is of extreme
importance to the perfumer. It exists in minute quantities in
the essential oils of ylang-ylang, champaca, and nutmeg. It is,
however, produced on an enormous’ scale by the isomerisation of
eugenol (see “ Eugenol ” and “ Carnation ”) as an intermediate
step in the manufacture of that most important substance,
vanillin, from oil of cloves. A considerable quantity, however, is
sold as such to perfumers for the manufacture of artificial carnation
and similar perfumes. Its odour, being somewhat “ heavy,”
adapts it to the preparation, when suitably blended, of perfumes
of the so-called Oriental type.

Isoeugenol is a pale yellow to colourless oil of powerful clove-
carnation odour, having the following characters : —

Boiling point at 760 mm. . . . 263°

Boiling point at 4 mm. . . . 112°

Specific gra-vity .... 1-089

Refractive index . . . . 1-5736

Optical rotation . . . .0°

When cooled to a low temperature, isoeugenol solidifies, and
melts at 34°, but as commercial sp'ecimens invariably contain
traces of impm'ities, it is always liquid, in a state of superfusion.
The industrial preparation of isoeugenol is a matter of considerable
magnitude, and numerous patents have been taken out for its
manufacture. In the early days of vanillin manufacture the

356 ' 23-2

PERFUMERY

principal difficulty was the fact that in the isomerisation process
isoeugenol showed a great tendency to give rise to polymerisation
products and tarry matters. The principal methods which have
been used are the following. In 1890 Haarmann and Reimer
(German patent No. 57808) recommended heating the eugenol
with a satm'ated solution of caustic potash in amyl alcohol. The
temperature is maintained at 140° for about twenty-four hours.
The isoeugenol is tlirown out of solution bj'- the addition of a
dilute acid, and rectified. De Laire (French patent of 1890,
No. 209149) recommended as an alternative, heating in an auto-
clave to a temperature of 100° to 100° of a concentrated soffition
of potassium-eugenol. Kolbe (French patent of 1891, No. 213892)
preferred an ethyl alcohol solution of caustic potash for isomerisa-
tion. Einhorn (German patent No. 76982 of April 5th, 1892)
recommended the use of anhj'-drous caustic potash with eugenol
at a temperature of 230°. The jneld is proportional to the rapidity
vdth which the mass is heated to the maximum temperature.
Schleich (French patent No. 239197 of June, 1924) prefers to heat
the eugenol with a glycerine solution of caustic potash for six
hours at about 230°.

Einhorn’s process is one wliich gives a very satisfactory 3 deld,
and is ver}'- commonly employed. The oxidation of isoeugenol
■mil be dealt with under “ Vanillin.” Isoeugenol forms niunerous
crystalline compounds which serve for its identification. Blono-
bromisoeugenoldibromide melts at 138° to 139°. If eugenol be
aeetylated for five hours, acctjd-isoeugenol results, which, if
dissolved in benzene and precipitated by petroleum ether, melts
at 79° to 80°. Benzoyl-isoeugenol is prepared by the interaction
of isoeugenol, benzoyl chloride, and caustic soda. It melts at
104° to 105°. Isoeugenol also forms a diphenjd-ui'ethane melting
at 112° to 113°.

Isoeugenol usually gives the best results when used in con- .
junction with a little eugenol, the former having a more typical
carnation odour, and the latter a more typical clove odour. This
mixtm’e is quite indispensable in the preparation of perfumes of
the “ ceiUet ” type.

ISOGERANIOL. — ^This body is an alcohol having a sweet
rose odour, resulting from enolising eitral with acetic anlij'-dride.’
An internal rearrangement of the position of a double bond thus
takes place, and the acetic ester of ewoZ-citral results. By. the
reduction of this body by means of sodium amalgam, and methyl
alcohol slightly acidified -with acetic acid, isogeraniol results.

3oG

PEBFUMEm

Isogeraniol boils at 103° at 9 mm. pressure, and lias a specific
gravity 0-879 at 20°, and refractive inde.v 1-4730. It forms a
diplienyluretbane, melting at 73°, and an oily tetrabromide.

ISOPROPYL ALCOHOL. — Vide “ Alcohol, Isopropyl.”

ISOPROPYL-o-CRESOL. — ^Tbis is a synonym of earvacrol
[q.v.). •

^ ISOSAFROL. — ^This body is the methylene ether of propenyl-
dioxy-benzene, so it is related to safrol, 'u'hich is the methylene
ether of aUyl-dioxy-bcnzene, in the same manner as isoeugenol is
to eugenol. Isosafrol, CioHjo02, is a higlily odorous liquid, having
a specific gra^vuty l-12o5 ; boiling pomt, 254° ; refractive index,
1-5780. It is optically inactive. Both safrol and isosafrol jdeld
heliotropin (g.-y.) on oxidation, but as a much higher yield is
obtained from isosafrol, the conversion of safrol into isosafrol is
always a preliminary step in the manufacture of heliotropin.
Safrol constitutes the principal part of oil of sassafras, but as it
exists in considerable quantity in camphor oil, the commercial
supply is derived entirely from the latter oh. Safrol is heated
for twenty-fonr hours with 2-5 parts of caustic potash and 5 parts
of 90 per cent, alcohol. At the end of this period an excess of
water is added, and after recovering the alcohol by distillation,
the reaction mass is extracted with ether. The isosafrol so
obtained is dried over calcium chloride and rectified. Variations
in the methods of isomerisation are similar to those for eugenol.
{Vide “Isoeugenol.”) Isosafrol is actually a mixture of two
stereoisomers.

Hbring and Baum {Berichte, 4S, 3076) have succeeded in
isolating these two isomerides. _ They have worked vdth the
isosafrol of commerce, which is a mixture of a- and /3-isosafrol
with safi’ol. ^-Isosafrol is contained in the fractions of high
boiling point, from which it may be extracted in the pure state,
oving to its property of forming a stable picrate, melting at 74°.

/9-Isesafrol may be separated from the safrol with n’hich it is
mixed, by the formation of a mercurial compound, which is
produced by the action of mercuric acetate and calcium cliloride.

The characters of the two isomerides are as follows : —

a-Isosafrol

Boiling point (743 mm.) . . 241°-242-5°

Specific gi-a-vity at 18-5° . . 1-1073

Refractive index at 18° . . 1-5678

357

r JiJ li 1<‘ U IVl E K X

ji-Isosafrol

Boiling point (743 min.) . . 2ol°-251*3°

►Sjiccific gravity at 17*5° . . 1*1227

Refractive index at 18° . . 1*5786

ISOSANTALENE.— Sec " Santalene.^'

ISOVALERIANIC ALDEHYDE.— This aldehyde, of the
formula CH 3 .CH(CH 3 )CH 2 .CHO, has been isolated from American
peppermint oil. It is a volatile liquid, boiling at 92*5°, and having
a specific gravity 0*804. It forms a thiosemicarbazone melting
at 53°.

IVA OIL. — See “ Achillea Moschata.”

JACINTHS. — = Hyacinth (q.v.).

JARACANDA. — ^This is a native name for hois de rose {q.v,). ■

JASMAL. — See “ Phenyl-gtycol-methjdene-acetal.”

JASMINE. — ^The perfume of this beautiful flower has always
been highly esteemed. The flowers are cultivated to a large extent
in the south of France, the crop beuig gathered almost continuously
from Juty to October. The jasmine is a member of the natural
order Oleacece, and is probably a native of India. Donald
McDonald (“ Fragrant Flowers and Leaves,” 1895, 59) gives the
follovdng account of the introduction of the jasmine plant into
Italy, which is probabty only legendary. One of the early Dukes
of Tuscany was the first o^vner in Italy of a plant, and as he wished
to retain it as a novelty, he forbade his gardener to give awaj^ any
cuttings of it. The gardener, however, disobeyed his orders and
gave his mistress a bunch of, the flowers as a birthday offering.
She was so pleased vith their perfume that she struck some of
the branches, and b 3 '' careful cultivation produced large quantities
of flowers, which she sold to such advantage that she amassed
a fortune and married the gardener.

There are about 100 species of jasmine recognised, mostly natives
of Lidia, Arabia, or Cliina. The species principally cultivated in the
south of France for the perfume is Jamnimim grandijlorum, the
so-called Spanish or Catalonian jasmine ; it is usually grafted on
to cuttings of Ja-sminum officinale. The cuttings are allowed to
become well developed, and as soon as they are strong enough the
yellow plants are grafted on, and the plants are left to their
second j’ear. The flowers are picked as soon as possible after thej'
open, Avliich is usually in the evening in duty to the middle of

.3.5S

PERFUMER 7

August, and in the earty morning after that time. The essential
oil of jasmine is not prepared on a commercial scale, the natural
jasmine perfume being marketed as an enfleurage or similar pro-
duct. A ■ver3’’ large amount of the jasmine perfume of commerce,
however, is partialh* or enthel}^ artificial.

-The jasmine plant and its perfume has been of considerable value
in tracing the development of the perfume in the plant tissues.
Hesse, for example, has shovui that when the flower is extracted
bj means of a \ olatilo solvent the essential oil does not contain
either niethj-l anthranilate or indol, whereas when extracted bj?
the enfleurage process, so that the life processes in the flower can
continue for some time, there is a prolonged production of essential
oil due to the decomposition of a glueoside, and not only is a
laigci yield of essential oil obtained, but both mcthj'l antlmanilate
and indol api^car as new constituents of the oil, (See also Charabot
and Gatin, “ La parfum choz la plante,” Paris, 190S). Niviere
(Bull. SoG. Chim., 1920, 37, SG2) has shovm that if the jasmine
flov'ers are submitted to a preliminary hych-olj'sis by acids or
enzjmies before extraction with a volatile solvent, a higher jnold
of oil is obtained. Mesnard has also used the jasmine flower for
his investigations { Kccherchcs sur le mode de production du
parfum dans les fleurs ” : E. Jlesnard, presentee a 1’ Academic par
Duchartre, Gompics Rendns, 1892, cxv., 282). He states that in
the jasmine flower, the essential oil is situated in the row of
epidermal cells on the upper side of the sepals and petals. Some
exists also in the corre.sponding laj'^er on the under surface, where
the sepals are colom’cd by a violet pigment. If the evolution of
the cell contents in flowers at different stages of development be
foUowed, at first nothing but chlorophjdl is found in the tissues.
Tannic acid next appears, or glucosides which jdeld tannic acid
on hj^drolj’^sis. These glucosides also yield the pigments of the
lowei surface of the sepals. Hydrocliloric acid gas serves as a
reagent to distinguish between the intermediate compounds
between the chlorophyll, on the one hand, and the tannic acid,
pigments, and essential oil on the other. Apparently in the lower
sm-face, which in the bud state was exposed to the fight and air,
the intermediate tannoid bodies are slowty oxidised and give rise
to tannic acid, whilst on the upper surface, being hidden inside
the bud, these agencies are inoperative, and the same compounds
are decomposed in a different manner with the production of
essential oil.

Jasmine oil obtained from the pomade varies considerabty,

' 359

PERFUMERY

according to the exact method of production. The specific
gravity may be as low as 0-920 or as high as 1-015. The optical
rotation lies between — 1° and + 5°, the ester value between
40 and 72 per cent., calculated as benz 3 d acetate.

Verley {Comxites Rendtis, 1899, 128, 314 ; Soc. Chiin., 1899,
iii., 21, 226) investigated the oil extracted from the pomade
by means of acetone, and stated that the oil consisted of approxi-
matety 10 per ‘cent, of linalol and 90 per cent, of phenyl -gl 3 ’-col-
methylene-acetal, which he termed jasmal. The result of this
work was a French patent for the production of jasmal synthetic-
alty. Hesse and Muller {Berichie, 1899, 32, 565, 765) showed later
that tliis bod 3 '- did not exist in jasmine oil. They found then (and
later, Berichte, 1901, 34, 291) that the oil had the following

composition : —

Per cent.

Benz 3 d acetate . . . . .65

Linal 3 d acetate ..... 7-5

Linalol . . . . . .15-5

Benzo 3 d alcohol ..... 6

Indol ...... 2-5

Jasmone . . • . . . -3

Meth 3 d anthranilate .... 0-5

Traces of para-cresol and geraniol are also probably present.
Hesse and Muller {loc. cit.) give the following characters for ten
samples of oil which they examined : —

Specific

gravity.

Potation.

Esters as benzyl
acetate.

1 .

1-015

+ 2° 30'

Per cent.

2 .

+ 2° 30'

3 .

+ 2° 30'

72-9

4 .

+ 3° 30'

70-4

5 .

+ 3° 15'

69-1

6 .

+ 3° 10'

70-7

7 .

+ 3° 20'

8 .

+ 3° 10'

9 .

+ 3° 30'

■■

1-015

+ 3° 20'

71-4

The body jasmone is a ketone of the formula CnHigO, of
specific gravity 0-945, boiling at 258°' at a pressure of 775 mm.
It yields an oxime melting at 45°, and a semicarbazone melting at
201° to 204°.

360

PERFUMERY

The commercial product sold as jasmine oil (apart from the
absolutes and concretes) is artificial, and is based invariably on
benzyl acetate, which has a maiked odour of the flower. Some-
times tliis ester is modified with a little benzyl formate and a little
linalyl acetate. Tree alcohols, linalol, benzyl alcohol, and traces
of geraniol are usually present, and traces of benzyl propionate,
cresylphenj’lacetate, and phenjd-ethyl alcohol are often used.
A little method antliranilate and indol are generally employed,
unless an absolutely colourless product is desired, when the indol
must be omitted. Traces of decyhc aldehj^de, phen 3 dacetic acid,
and a little natmal jasmine will improve the artificial product
considerably.

•Jasminum odoratissimum is a native of Madeira which is
cultivated in Formosa for the purpose of perfuming tea. The
yellow flowers, wliich retain their perfume when dried, are known
as Shuei flowers.

Er. Tsuchfliashi and S. Tasaki {Jour. Soc. Cliem. Ind., 1919, 38,
117) have treated these flowers by means of petroleum ether and
obtained a solid essential oil with a jdeld of 0-277 per cent. This
solid, exhausted with alcohol, yielded 0-116 per cent, of essential
oil and 0-T61 per cent, of wax.

The essential oil thus obtamed is a reddish-brown liquid, vTich
has the following constants : —

Specific gravity ..... 0-9309

Optical rotation . . ... . -j- 5-64°

Refractive index ..... 1-4845

Acid value . . . . . . 5-85

Saponification value .... 92-25

Saponification value after acetylation . 186-20

It distils between 60° and 200°, and its composition is as
follows : 6 per cent, linalol, 6 per cent, linalyl acetate, 1-6 per cent,
benzyl alcohol, 6 per cent, benzyl acetate, 10 per cent, method
antlu-anilate and indol.

Fifty-seven per cent, of the oil is composed of a diterpene and a
sesquiterpene alcohol, w-hich are found in the fractions with
high boiling points. The authors found no jasmone in tliis
essential oil.

Treatment of the flowers of Jasmimim odoratissimum by
enfleurage in the cold gave no result.

J asminum sambac is -a native of Arabia which grows 'wild in
profusion in India. Its flowers are delightfully fragrant. The
so-called Tuscan jasmine is Jasminum trifoliatum, knowm in India

361

PERFU MER 7

as hadda-mulla. Numerous other species bear very fragrant
flowers, but their perfume is not extracted.

J ONQUIL. — ^The jonquil is Narcissus Jonquilla (see “ Nar-
cissus ”), one of the liighly-scented flowers of the natural order
Amariillidacece. The natural perfume is extracted b}'' the en-
fleurage process, and can also be produced as a concrete, but the
essential oil is not manufactured. Ai’tificial jonquil is very
similar to artificial narcissus and hyacinth {q.v.). As a rule,
however, phenyl-ethyl phen 3 dacetate is used in jonquil vdth a
trace of iDatchouli oil.

JUNIPER OIL. — Juniper oil is the distillate of the berries of
Jwiiqjerits communis, one of the Goniferce, growing commonly in
many jDarts of Europe. The oil is only used to a very limited
extent in actual perfumery, but is used to a considerable extent
in the allied industry of flavouring liqueurs and cordials. Jmiiper
is the basis of all gin flavours. The common juniper is a native
of Greece, forming a small shrub in most parts of Europe, but
growing to 30 or 40 feet high in Scandinavia. Schinuncl cb Go.
give the following as the average ^dcld of oil from juniper berries
of various origins : —

Bavarian .
Thuringian
Italian
Hungarian

Per cent.
1-2
0-7
1-1*5
0-S-l

Per cent.

East Prussian . 0-6

Swedish . . 0-5

Polish . . 0-9

Much of the juniper oil of commerce is deprived of its prmcipal
flavouring ingredients, so that it is really onlj’ a light oil of juniper
containing little other than terpenes. Juniper oil contains pinene,
camphene, cadinene, and a small amount of oxygenated con-
stituents. Amongst these latter is terpinenol and an alcohol not
yet identified, but having a specific gravity 0-9476 ; ojitical
rotation, — 4° 30' ; refractive index, 1-4835 ; and boiling point,
218° to 226°. It is in all jwobabihty a sesquiterpene alcohol.
Traces of esters are also present.

Juniper oil is an oil which rapidly oxidises on keeping, vdth the
formation of insoluble constituents. An oil kept under fair
average conditions will have the following characters : —

Specific gravity . ..
Optical rotation
Refractive index
Ester value . . ' .

Ester value after acetylation

362

0- 865-0-890
— 3° to — 20°

1- 4750-1-4880

2-8

15-25

PERFUMERY

Occasionally a sample is found to be dextrorotatory to the
extent of -f- 1° or -p 2°. Samples ■«dth specific gravities above
0-S90 are usually so old as to be of little flavouring value.

The essential oil distilled from the berries of .hiniperus jyhcentcea,
v'hieh is foimd in Sardinia and C\*prus, is higlil}’’ aromatic. It has
been examiiaed by Puxeddu and Vodret {Gciz. Chim. liah, 1920,
50, ii., 245—257), vho state that, vhen distilled vith water, the
macerated berries of the plant yield 2-5 per cent, of essential oil,
fom’-fifths of this amount distilling over during the first horn,
wliile the remainder requires about five hours ; the preliminary
maceration with water should last at least two days. The oil is
neutral, colourless, and transparent, but turns slightly yellow
under the influence of light. Its taste resembles that of camphor,
and it has a marked aromatic odour, while when rubbed between
the hands it emits the odour of turpentme. It burns until emission
of dense smoke and resinous odour. It has a specific gravity
— 0'8G5S at 15° C., and specific rotation -|- 1G"84°.

K/EMPFERIA ETHEL^^E. — ^The essential oil distilled from
the tubers of Kmmpferia EtJidcc, a plant belonging to the natural
order Zingihcraceoi, has been examined by Goulding and Roberts
{JouT. Clioin. SoG., 1915, 314). The yield was about 2 per cent,
on the dry material, of an oil having an odour somewhat resembling
that of neroli oil, with a suggestion of crushed ivy leaves. The oil
has the following characters : —

Specific gravity . . . 0-923-0-944

Optical rotation . . . + 19° 47' to + 30° 4'

Acid value . . . 1 •0-2-3

Ester value . . . 5-11-5

Ester value after acetylation 33-G-47-6

The dried bulbs, or tubers, which occur in north-eastern
Transvaal, are there known as Slicnmgulu.

The composition of the oil is given as follows : —

_ Per cent.

Terpenes . . . , , ,21*8

Cineol ! 17-2

Ksempferia ketone . . . .13-0

Alcohols (including linalol) . . . 11.2

Esters (chiefly methyl anthraniiate) . 1-3

Phenols •-.... 0-5

Acids (free) . . . . .0-1

Residue (chiefly sesquiterpene) . . 34-9

The ketone present in this oil is a crystalline body, of the

363

PERFU MERY

formula Co^HosOdi melting at 102°, and having a specific rotation
-}- 198° in cliloroformic solution. In dilute alcoholic solution
this body has a distinct odour of crushed ivy leaves. It yields
a hj'droxylaminc oxime meltmg at lSd°, and an oxime melting
at 106°.

K/EMPFERIA GALANGA.— The roots of this species of
Kcem,j)Jcrki yield a heavy essential oil of specific gravity about
1*025 ; optical rotation, — 10° ; and refractive index, 1*5428.
It contains ethyl cinnamatc and eth 3 d-^fira-mcthox 3 '-cinnamate.

KAOLIN. — This substance is used to a small extent in the
preparation of toilet powders, and also to some extent as a filtering
powder. It is a white or gre 3 dsh-whitc porcelain cla3^ resulting
from the decomposition of felspathic rocks, and consists mainl 3 '
of one or more silicates of aluminium, with small quantities of
other inorganic substances.

KAPUR-KACHRI. — The dried root of Ilcdycliivm spicaium,
an Oriental plant belonging to the natural order Zivgihcraccce, is
much valued in the East, cspccialh' b 3 ' the Arabs and Persians, as
a perfume, and is used b 3 ^ the Hindoos as incense for ceremonial
purposes. The name (see Sawer, Odorograpliia,” series ii., p. 72)
is derived from the Grcclv, and means “ sweet show,” in allusion to
the elegance, fragrance, and whiteness of the flowers of the first
named species of the genus, Hcdychium coronarium. II. spicatum
is a native of Sepal and Silhet, and is fairl 3 ^ common in the Punjab
Himala 3 ’-as. According to D 3 'mock, the dried root forms a con-
siderable article of commerce in India and China, and is also
exported to Europe. Two varieties arc Avell recognised, the
Indian and the Cliinese. Tlic Indian kapur-kachri was formerly
believed to be identical with the so-called “ lesser galangal root,”
but this is now known to be incorrect. J. T. Thresh {Pharm. Jour.,
3, XV., 361) describes the odour as intermediate between storax
and rhubarb root, whilst D 3 miock prefers to sa 3 ’- that it recalls
that of orris root and camphor. Thresh {loo. cii.) states that the
amount of actual odoriferous material is vcr 3 ^ small, but that it is
ver 3 ’- powerful. A minute quantit 3 ’-, exposed to the air, recalls the
odour of h 3 ’’acinths. He extracted the roots with petroleum ether.
On allowing the solvent to evaporate slow] 3 ’’, a crop of large,
colourless, tabular ciystals was obtained, which when recr 3 ^stal-
lised, melted at 49°. Tliis body appears to be cth 3 d-meth 3 d-
paracoumarate, but it is not the odoiu’ bearer of the root, which
has not been isolated and identified. Numerous other species of

304

PERFUMER Y

liedycliiiim are cultivated, but liave not been examined to any
extent, from them perfume point of view. The essential oil of
Eccli/clii 11771 C07 07i(i7'i7(772 has been found to have a specific gravity
0-S69, and an optical rotation — 0° 28' {ScUminel cD Co., Berichf,
April, 1894, 58). A Brazilian j)lant of tliis species was found by
Peckolt (Pharin. Rv77cl Few York, 1893, 11, 287) to have similar
characters.

KESSO OIL. — ^Ixesso'. oil is the name given to Japanese
valerian oil, distilled from the roots of Valeria 7 ia offichialis, var.
angiisiifoha. The jueld is liigh, sometimes reaching as much as
8 per cent. This (and other valerian oil) is used to a small extent
in certain soap perfiimes. The Japanese oil has the following
characters : —

Specific gravity . . . 0-965-1-000

Optical rotation . . . _ 20° to — 35°

Refractive index . . . l-4775-l'4875

Acid value .... 1-20

Ester value . . . 90-135

It has been examined by Bertram and Gildemeister {Arch, der
Phai'in., 1890, 228, 483). These chemists have identified the
following bodies in the oil : pinene, camphene, dipentene, ter-
pineol, borneol, bornyl acetate, bornyl iso valerianate, a sesquiter-
pene, a blue oil not yet identified, and an ester which has been
termed kessyl acetate, CJ4H23O.COOCH3. This body is the acetic
ester of kessyl alcohol, C14H24O2, a crystalline body, melting at
85°, and boiling at 300° to 302°. The acetate boils at 179° at
16 mm. pressure, and has an optical rotation — 70° 6'.

KOBUSHI OIL. — ^The fresh leaves and branches of the
Kobuslii tree {MagiioUa Koiu-s) yield about 0*45 per cent, of a
odorous essential oil, of specific gravity about 0-964 ;
optical rotation, — 1° 6' ; and ester number, 8-9. It has an odour
of sassafras. The oil contains eugenol, cineol, citral, methyl
chavicol, and other bodies. The tree flourishes in central Japan.
(See “Magnolia.”)

KUNZEA GORIFOLIA. — ^This plant is a very common
so-called “ tea tree ” growing in the Port Jackson district
in Australia, and although it . has become less plentiful than
it used to be, owing to the rapid spread of population, many
luxuriant patches are still to be found in the neighbourhood
of Sj dney . The leaves and terminal branchlets yield a very

365

PERFUMER Y

fragrant essential oil, whicli lias been investigated bj^ F. R.
Morrison {Jour, and Proc. Roy. Soc. of N.S.W., 1923, Ivi,, 201).

A total weight of 387 kg. of leaves and terminal branchlets, cut
as for commercial distillation, was submitted to distillation •with
steam and gave an average percentage yield of oil of about 0*35
per cent., varying from 0-2G to 0-52 per cent. The highest per-
centage yield was obtained from material collected at Waveiiey,
on the sea coast, the other localities being some distance there-
from.

The 3S7 leg. of leaves and terminal branchlets gave on steam
distillation crude oils possessing physical and chemical character-
istics as follows : —

Date.

Locality from
which material
was obtained.

Wciftltt of
lcavi‘S.
KWob.

Percent-

age

yield.

Specific
Rravlty at
15/15°.

Optical

rotation.

Pofract Ivc
index at
20’.

27/1/1921

Gore Hill

154

0-26

0-9103

+ 18-6°

1-4902

10/10/1921

Waverlcy

174

0-52

0-9112

-k 12-0°

1-4893

20/7/1922

LongueviUc >

0-32

0-9087

-k 24-0°

1-4837

5/10/1922

Hornsby

0-28

0-8917

-k 25-6°

1-4801

Ester no.,
hot
liours.

Ester no.
after acetyla-
tion. hot

1^ hourt'.

E^tor no.
after acetyla-
tion. cold

Z hours.

Solubility of oil In 80 per cent,
alcohol (by weight).

Colour of oil.

13-0

49-22

Insoluble in 10 vols.

Brovm

9-94

57-58

31-78

Insoluble in 10 vols.

Dark bromi

15-48

66-66

34-89

Soluble in 10 vols.

Light green

13-66

39-19

15-57

Insoluble in 10 vols.

Light brown

The crude oils, on distillation, gave the following results :
January 27th, 1921, 32 per cent, distilled between 40° and 50° at
10 mm. ; 5 per cent, between 50° and 100° ; and 54 per cent,
between 100° and 140°. October 10th, 1921, 36 per cent. distiUed
below 185° at 762 mm.

Determination of the Terpene. — ^The lower boiling fraction in
each case was submitted to repeated distillation, over 80 per
cent, distilling below 160° at 766 mm. It was found to consist
principally of d-a-pinene, which gave the following constants :
January 27th, 1921, boiling point, 155° to 157° ; specific gravity
15°

— , 0-8613 ; optical rotation, -f- 40-6° ; and refractive index 20°,
15

1-4655. October 10th, 1921, boiling point, 155° to 157° ; specific

366

PEBFUMERY

gravity 0‘8G23 ; optical rotation, -f- 39"9° ; refractive index
20°, 1-4C51.

Confirmatorj^ evidence of its identity vas established by
preparation of tlie folloving derivatives : —

^ On acctynt of the high optical rotation the terpene failed to
give a nitrosochloride ; on mixing, however, with an eqnal
volume of /ccro-pincne (a)j, - 50-18°, which by itself faded to
give a nitrosochloi’ide, an excellent 3’iGld of the derivative was
obtained wliich, Avhen purified, melted at 104°.

The hydrocliloride, irrepared by saturating 5 c.c. of the' ter-
pene at — 20° with dry hj’drochloric acid gas, resembled camphor,
and after recr^ystallisation from alcohol, melted at 127°.

Oxidation of the Terpene . — 58 c.c. were shaken with 120 grams
of potassium permanganate, 1,000 c.c. of water, and 500 grams of
ice until completion of reaction. The liquid was passed through
a suction filter, whereby the manganese sludge was removed,
and the cltyr liquid then evaporated to small bullc. It was their
steam distilled in order to remove unchanged terpene, and again
concentrated by evaporation. Dilute sulphmic acid was then
added, the liberated pinonic acid extracted vith chloroform,
whrj;h latter solvent was distilled off, and the crude acid distiUed
at 5^ mm. pressure, when the greater portion came over at 180° to
181 C. After standing for some considerable period crystals
separated, and these were removed by filtration. On recrystal-
lisation from petroleum ether the crj-stals melted at 68°;
0-1704 gram of the pure acid dissolved in 10 c.c. chloroform
rotated the plane of polarised light -f 1-7°. Specific rotation,
(a)i, + 100°. The semicarbazone was prepared, and after re-
crystallisation from alcohol melted at 207° C. The terpene is
therefore d-a-pmene. ^

Deterniination 0/ the Sesquiterpene. — ^That portion of the Gore
sample of oil distilling between 100° to 140° (principally
120° to 140°) and the higher boiling portion of the Waverley
sample were allowed to stand over metallic sodium for a week
and repeatedty'frtytionated over that metal rmtil a main fractioir

was obtained, which possessed the follovdng characters ;

Gore Hill .- boiling point, 129° to 132° at 10 mm.'; specific

gravity -j— ^ 0-9218 ; optical rotation, -{- 6° ; refractive index

at 20°, 1-5056.

Waverley: boiling point, 129° to 132° at 10 mm.; specific

367

PERFUMERY

gravity ’ 0-9239 ; optical rotation,

refractive index

at 20°, 1-504G.

Pre 2 xiralion of ilia Hydrochloride. — Five c.c. of the sesquiterpene
were dissolved in 10 c.c. of perfectly dry ether, the vessel placed
in a mixture of ice and salt at — 20°, and the solution saturated
mth dry hydrochloric acid gas. It was allowed to stand over-
night, when erystals separated. On recrystallisation from alcohol
they formed beautiful needles, melting at 116° to 116°; 0-1162
gram dissolved in 10 c.c. chloroform gave optical rotation
- 0-65° (a)j, - 39-11°.

The sesquiterpene which gives a corresponding derivative with
h 3 ’’drochloric acid gas to that obtained as above, is cadinene,
which, according to Parry (“ Chemistry of Essential Oils, 2nd ed.,
p. 73) possesses the following eharacters : boiling point, 272° to
275° at atmospheric pressure ; specific gravity, 0-9215 ; refractive
index, 1-5065 ; optical rotation, — 105° ; melting point of di-
hydi’ochloride, 117° to, 118° ; and specific rotation in cliloroform
solution, — 37°.

Attempts to prepare the nitroso chloride and nitrosate were
unsuccessful, but the evidence so far obtained indicates that the
sesquiterjDene occurring in the oil is probably identical with
cadinene.

Alcohols. — The saponification values after acetylation of the
crude oils indicate the presence of fair quantities of alcoholic
bodies in the oils. The only portion, however, in which these
bodies appeared to be concentrated was a small fraction boiling
between 160° to 185°. This fraction was shaken with 50 per
cent, resorcin solution, and on steam distillation 5 c.c. of a light
blue oil were obtained which had the characteristic fragrant odour
possessed to a lesser degree by the crude oil. The constituent
thus obtained had the follovong characters : specific gravity

, 0-9029 ; optical rotation, -j- 6-2° ; refractive index at 20°,

1-4685.

KUROMOJI OIL. — The leaves and young twigs of the
Japanese plant Lindera sericea, one of the Lauracece, yield an
essential oU having a very fragrant odour recaUing that of the
myrtle. The native name for the shrub is Kuro-moji, an allusion
to the very dark colour of its bark.

The oil obtainable in commerce is that distilled from the leaves
and young twigs, and is a dark yellowish oil of powerful balsamic

3G8

PERFUMER T

odour. It has a specific gravity O-SGO to 0-915, and is usually
sliglitl}' huvorotatory. It has been investigated by Kwasnik
{Arch, dll Pharin., 1892, 230, 2G5) and found to contain tf-Iiinonene,
dipentenc, tcrpineol, and carvone. An oil distilled by ScJiimmel
cO Co. from similar material was found to contain 9-5 per cent, of
est-ers calculated as geranjd acetate. Linalol was also detected
in the oil. Sbinobara has recently bivcstigated this oil. and states
that it contains 11-4 per cent, of esters, 20 per cent, of free alcohols,
7-7 per cent, of cineol, 51 per cent, of terpenes, 9-2 per cent, of
aldeb 3 'des and ketones, and traces of phenols and free acids. The
free alcohols consist of linalol and geraniol. The oil distilled from
the remainder of the shrub was also found by Schimmel <£• Co.
{Boricht, April, 1904, 98 ; 1907, G7) to contain cineol, hnalol,
geraniol, and geranjd esters.

LABDANUM. — ^This resinous material is an exceedingly valu-
able raw material for the perfumer. It has for man\^ 3 ^oars been
used in the Near East as a fumigating perfume, and has in recent
3 '^ears become ver 3 ’’ much esteemed as a perfume material in
western Emrope and America. It is an oleoresinous substance
obtained from species of Cistiis. In olden days labdanum was very
lughl 3 ’’ appreciated as a medicament. Its resinous, balsamic, and
stimulating properties caused it to be used in ailments of the
stomach and liver, and also as a remedy against loss of hah’. It
is to-day used, inter alia, as an ingredient in some t 3 ^pes of fumi-
gating pastilles — pastilles du Serail. The principal species from
which the oleo-resin is obtained are Cislus ladan ferns and Cistus
creticus, which are found dispersed all over the island of Cyprus,
and Cistus monspeliensis, which is found in Greece. Cistus ladani-
ferus is also found in Portugal and Spain. Several hybrids are also
knovTi which 3 deld a certain amount of the oleoresin. Formerly
the oleoresin was collected by the shepherds combing it from the
fleeces of sheep that had been browsing amongst the cistus
bushes and so loaded their wool with the sticky exudation. In
Crete a special instrument is used for collecting the resin which
is called a ladanisterion, a sort of double rake mth leathern thongs.
It appears that this method of collecting labdanum does not
differ materially from that given by Dioscorides in the first
Century (Tournefort, “ Voyage to the Levant,” i., pp. 56-GO,
London, 1718). To-day the sheep are not troubled much, and the
collection is almost entirely by means of- these leather rakes,
which are used to rub against the 3 munger parts of the plant and

p- 369 24

PERFUMBBY

then rubbed in sand to facilitate the removal of the resin.
Sometimes, also, the branches arc boiled in water and the resin
skimmed from the surface. The plants yield the oleo-resin most
freely from May to Juty, and round about noonday is the best
time for collection.

Holmes (P. ch E. 0. R., 1911, 155) has shown that Spanish
labdanum is obtained from Cistus ladanijcrus var. macellaius.

The botanical characters of the principal Cistus species have '
been studied recently b,y A. Camus [Bnllctiii, Roure-Berlrand Fils,
October, 1920, 3). Labdanum occurs in dark brown to blackish
viscid masses with a heavy languorous odour recalling the heavj''
type of Oriental perfume. It softens on handling, and exhibits a
grejnsh surface vdien broken, which quickly becomes black on
exposure to the ah’. It is, of course, insoluble in water, but is
almost completely'’ soluble in alcohol. It is sometimes adulterated
with cheaper resins. Very few authentic samjhcs of labdanum
have been examined, so that the following values must be accepted
with reserve. Dietcrich (” Analysis of Resins ”) gives the following
figures : —

Acid

value.

Ester

value.

! Saponification

1 value.

French commercial

90-37

116-1

206-47 •

91-98

120-26

212-24

98-05

102-06

200-11

98-36

109-88

208-24

German commercial

54-08

167-87

221-95

54-69

161-95

216-64

54-01

166-88

220-89

51-85

168-39

220-24

Cretan commercial

113-81

87-88

201-69

114-80

87-98

202-78

E. J. Emanuel' has examined this substance, and gives the
following as its characters : —

Per cent.

Resin extracted by ether . . .48

Resin by alcohol after ether . . .17

Essential oil ..... 2

Ladaniol (guaiol ?) . . . . 0’8

Gum ....... 3’5

Mineral matter . . . . .12

' The most recent and authentic contributions to the know-

370

PERFUMERY

ledge of labdaniim are those of Gcrarclin {Bitll. dcs Sciences
pliarmacohgiques, 1919, 6, 289), and Gerardin and Gaitefosse {La
Parjumcrie Moderne, 1920, 6, 111).

According to Gerardin, labdanum was formerly placed on the
market in the following forms ; —

“ In cakes, sticky and blackish lumps.

“ In small balls, the best coming from Cyprus (Schroder,
seventeenth century).

“ In twists or in cord.s. The material, dravm out into rods, was
twisted into the shape of a ram’s horn, or like tapers (cellar tapers),
Spanish liquorice, or chewing tobacco.

" Rolled w^arm, twisted and ornamented with designs (?). This
peculiarit}’ is met with in Llorelot’s ‘ Dictionnaire des drogues,’
1807, and is given by this author only.

“ In rods or magdaleons.

“ In bladders, where the material continued to assume con-
sistence. (Guibourt has thus seen a mass of 12 kg. of fresh and
soft material, with a peculiar, very strong and balsamic odour.) ”

Lastly, Poncelet (“ Chymie du gout,” 1755) describes it “ in
cakes for 'the hard part, in pliials for the liquid (balsam), and in
leaves of the shrub for the average part with the consistence of
thick syrup.”

Tw'o old analyses give labdanum the following compositions : —

According to Pelletier — Per

- Resin ...... 20-00

Gum with a little malate of lime . . 0-60

Wax ...... 1-90

Sand, ferruginous .... 72-00

OU and loss ..... 1-90

According to Guibourt — Per egnt,

Resin and oil . *. . . .86-0

Wax . . . ... . . 7-0

Aqueous extract . . . . .1-0

Earthy matter and hairs . . .6-0

The enormous differences apparent between these two results
are not surprising, considering the very impure state in which the
labdanum of commerce is marketed.

According to Parry (“ Chemistry of Essential OUs,” i., 503),
the oleo-resin contains 0-7 to 2 per cent, of an essential oil with
the following characters : —

Boiling point ' . . . 50°-185° under 15 mm.

Specific gravity . . . 0-928-1-011

Ilefractive index . . . 1-5100-1-5140

*71

i4 ' c

PERFUMERY

It oxidises rapidly on being kej)t, and deposits a large quantity
of crystals.

According to Masson {Gomptes Rendiis, 1912, 154, 517), this oil
contains acetophenone and a second ketone of the formula

CgHigO, whose constants are : —

Boiling point .... 178°-179°

Specific gravity at 0° . . . 0-922

Optical rotation . . . +0°

Befractive index at 23°. . . 1-4494:

Melting point of the semicarbazone 220°-221°

Masson also found in the oil extracted from the oleo-resin sonie
alcohols, phenols, and esters, while he indicates the probable
presence of guaiol.

The ketone CgHjeO is trimelhyl-l,5,5-hexanone-6.

The substance isolated by Emanuel, of the formula OjyHgoO,
which he named ladaniol, is, according to Parry, probably an
impure form of guaiol.

Rout e- Bertrand Fils have treated a certain quantity of Cistus
ladaniferus, gathered in the Esterel towards the end of December,
and obtained, on the one hand, a gum-resin of rather soft con-
sistence, coloured a deep green, and having a very marked
balsamic odour, similar to that of the labdanum from Cyprus.
On the other hand, by simple distillation and vdth a jdeld of
0-06 per cent., they obtained an essential oil of a golden yellow

colour, with a very strong and not disagreeable odour.

The characters of this oil were : —

Specific gravity at 20° . . . 0-9033

Optical rotation at 17° . . . •— 12° 10'

Refractive index at 12-5° . . 1-4800

Acid value ..... 3-7

Saponification value . . . 22-37

Ester value .... 18-67

Solubility in 90 per cent, alcohol . vol. to 5 vol.

The distillation waters, exhausted with petroleum ether, gave
a further 0-02 per cent, of an oil of a deeper colour than the former,
and whose constants were : —

Specific gravity’’ at 17-5° . . 0-9755

Optical rotation at 17° . . . — 2° 40'

Acid value ..... 18-67

Saponification value . . . 41-07

Ester value .... 22-40

Solubilit}’- in 90 per cent, alcohol . \ vol. and over.

The latter oil had a much finer odour than the du’ect oil.

372

PEBFU MER Y

Owing to the small amount of raw material at their disposal,
they were unable to obtain the oil of Oisiiis inonspcHiansis. Accord-
ing“ to ScJdmmel <h Go.- {Bericht, October, 1903, p. 81), tliis oU
has the following constants : —

Yield

Specific gravity at 15°
Optical rotation .
Acid value .

Ester value .

0'015 per cent.

0-9786

-f- 1°40'

15-7

31-51

It is of a clear browm colour, and between 20° and 25° deposits
a considerable proportion of paraffin, melting at 64°.

LANTANA OILS .—Lantana camara, a plant of the natural
order Ycvhcnctccoc, is vddely distributed in Java, Hew Caledonia,
and the Philippines, and grows wild bj’^ the roadside and on waste
lands tlu’oughout southern India. It is found all over Travancore
up to an altitude of 4,000 feet.

According to Moudgill and Vridliachalain (P. cfc E. 0. R., 1922,
173), the plant has been introduced into India from abroad. The
essential oil is pale yellow in colour, and has a pleasant aromatic
odour recalling that of sage. It has been examined by Kanga
{Journal of the InstiMe of Science, I., ix.), and also by ScJdmmel
& Co. {Report, October, 1896, and 1909). The most recent examina-
tion of the oil, however, is that of Moudgill and Vridhachalam
{loc. ciL).

Travancore oil
from leaves.

Kanga’s figures
from leaves.

Schiinmd
& Co,'s
Beport,
1909.

Specific gravity

(30°/4°) 0-8842

(24°/24°) 0-92114

0-9132

Rotation

-{- 14-7

' -j- i"96

-|- 11-5

Refractive index

1-4899

1-4S93 :

1-4913

Acid value

1-6

. —

—

Saponification value

4-6

—

Acetyl value .

23-4

—

Aldehj'de content .

2-4 j)er cent.

. Thc'plant was collected during November. Eour hundred and
fifty pounds of the air-dried leaves (moisture 12-5 per cent.) were
steam-distilled in a large copper still with false perforated bottom,
care being taken that the leaves did not come in contact with the
hot bottom of the stiU, and a 0-2 per cent, yield of a greenish-yellow

373

PEBFU MERY

oil possessing an oclonr "was pleasant and jDersistent, par-

ticulai’ly ndien considerably diluted "witli alcohol, "svas obtained.
It showca slight green fluorescence, and was soluble in five or more
volumes of 07 per cent, alcohol.

These constants would suggest that the oil consists principally
of hj’drocarbons, and that it contains very small proportions of
free alcohol and aldehyde. Further examination bears this out,
for the oil has been found to be of comparatively simple com-
position, containing about 10 to 12 per cent, l-a-phellanch’ene,
SO per cent, of a sesquiterpene much resembling caryophyllene,
and the rest a complex mixture.

The oil was fractionated under reduced pressure and, finall 3 q
three fractions obtained : —

(1) 55°— 75° at 12 mm.

(2) 75°-125° at 12 mm.

(3) 125°— 130° at 12 mm.

Residue

Per cent.

12 by volume
8 „

74 „

6 (calculated by differ-
ence).

Lantana odovata jnelds an oil having an amber odour. It grows
in J amaica and other islands of the West Indies.

LARD. — Lard is the purified fat of the hog, Sus scrofa. It is
used in the extraction of perfumes from flowers by the enfleurage
process, and is also used in the preparation of various cosmetics.
Whenever it is used, it is absolutely essential that it should be
of the very finest quality and free from fatty acids. Further, it
is important that free fatty acids should not develop in the fat,
and in order to keep it in good condition it is often digested in
the melted condition vnth gum benzoin, with constant stirring.
The fat thus takes up benzoic acid and other constituents from
the gum, and vill keep sweet for a prolonged period. Lard so
treated is known as “ benzoated lard ” or adej)s henzoatus.

Lard, which is produced on a very large scale in the United
States, is there classified as follows : —

(1) Neutral Lard No. 1. — ^This is obtained from the fat by
rendering the finely cut up mass at a temperature not exceeding
50°. Neutral lard No. 2 is similarly obtained from the fat taken

, only from the back of the animal.

(2) Leaf Lard. — ^The residues from which “ neutral lard ” has
been rendered yield, when subjected to a steam heat in an auto-
clave, the commercial variety known as leaf lard.

(3) Choice Kettle-rendered Lard. — ^This is obtained bj’’ rendering

PERFUMERY

tlie residues left from the preparation of “ neutral ” lard in open
steam jacketed vessels.

(4) Prime Steam Lard . — ^This term is applied to the fat rendered
from all the other parts of the hog at steam heat.

Genuine lard for perfumery purposes should be practically
neutral. It viU generally have characters falling udthin the
folloudng limits : —

Melting point .

Solidifying point

Saponification value

Refractomer number

Iodine value .

c 100°

Specific gravity

Unsaponifiable matter

35°-46°

25°-30°

192-199
49-52 at 40°

55-66

0-860-0-863

Less than 0-5 per cent.

It should not contain more than traces of water. Care should
be used in judging whether a given sample is free from cotton oil
or not, since the fat of hogs which have been fed on cottonseed
cake will usually give a slight reaction for cottonseed oil. There
are a number of fats found in commerce under the name of lard
substitutes. These are frequently mixtures of a liquid fatty oU.
with about 20 per cent, of the stearine of beef fat. (For the
detailed examination of lard, see “ Fatty Foods,” Bolton and
Ilevis, p. 101.)

LASERPITIUM OIL. — ^The fruits of a species of Laser-
pitium, a genus belonging to the natural order UmbelUferoe, yield,
according to Haensel {Chem. Zentral., 1906, ii., 1496), nearly
2 per cent, of a dark green essential oil having an odom recalling
those of aniseed and caraway. It has a specific gravity 0’9538 at ^
20° ; acid value, 3*2 ; ester value, 12-3 ; and ester value after
acetylation, 28-5. It contains limonene, eugenol, diliydroeugenol
methyl ether, and a paraffin hydrocarbon melting at 57° to 58°.

LATHYRUS ODORATUS. — ^This plant is the popular sweet
pea, a member of the natural order Leguminosce. A small amount
of the natural perfume may be found, but in the main the sweet
pea perfumes of commerce are synthetic. The essential oil occurs
in such minute proportions that it has never been systematically
examined. It certainly contains, however, methyl anthranilate.
In preparing sjmthetic sweet pea perfumes methyl antlrranilate,
benzylidene-acetone, hydroxycitroneUal, and terpineol are indis-
pensable. Numerous other synthetic perfumes are employed, and

376

are rounded off with natural essences, such as jasmine and
bergamot.

LAURIG ALDEHYDE.— See “ Aldehydes, Higher Fatty.”

LAUREL-LEAF OIL. — Lauriis nobilis, a tree belonging to
the natural order Laiiracece, possesses leaves having a sharp
aromatic odour. The oil, which is obtained to the extent of
from 1 to 3 per cept. from these leaves, has the following
characters : —

Specific gravitj’’

Optical rotation
Refractive index
Acid value
Ester value

Ester value after acet 3 da-
tion . . . ,

0- 915-0-930 (occasional!}’- higher)
— 15° to — 22°

1- 4G70-1-4775
1-5-4

20-53

36-100

The oil contains pincnc, cineol, linalol, geraniol,

eugenol, and methyl eugenol. Traces of a sesquiter^mne and a
sesquiterpene alcohol are also present.

LAVENDER, OIL OF. — ^As a raw material for the perfumer,
the essential oil of lavender is certainly amongst the most im-
portant, both from the j^oints of view of quality and quantity.
"N^ery large quantities are consumed in the manufacture of that
t}qDically English toilet perfume, lavender water ; a great deal is
used in the equally popular eau de Cologne ; and it enters into
iimumerable other perfume compositions, so that its consumption
is on a very large scale. France, of com’se, is the home of the
lavender. A small amount of exceedingly fine quality is grown
and distilled in England, but for aU practical purposes the world’s
supply is produced in France. This, of com-se, is not quite so true
of the spike lavender and its oil, since a considerable amount of
this oil is produced in Spain.

So important is this oil to the perfumer, that it is of interest to
trace the modern vieAvs of experts in reference to the plants from
which it is actually obtained.

The position, as conceived by him, is summarised by Lamothe
(“ Lavand. et Spic.,” 2nd ed., 1908) as follows : —

The principal lavender species are (1) Lavanchila laiifolia (L.
spica), also known as spilce lavender, or male lavender.

(2) Lavandula officinalis {L. vera) also known as the true
lavender or female lavender.

(In regard to Lavandula laiifolia, no divergence of opinion is to
be noted.— E. J. P.)

PERFUMER Y

Jordan, after a lengthy investigation, considered it necessary
to classify the true lavender {Lcuvcindula, ojjicinalis) into two
subdivisions, namely —

(а) Lavand/ida fragrans {lavande odoraoite ; lavande moyenne).
Tills variety, he stated, is vddely distributed, occurring at the
lower altitudes of growth.

(б) Lavandula Delpliiniensis {petite lavande ; lavande fine). This,
according to Jordan, is found exclusively in the highest regions
of growth.

In addition to these, Lamothe states that there occurs a cross
between Lavandula fragrans and Lavandula latifolia, which
Reverchon has named Lavandula Hyhrida, and Chatenier Lavan-
dula fragrans latifolia (or grosse^ lavande, lavande hdtard, lavendin,
or spigoure). Distillers, according to Lamothe, recognise these
varieties under the names (1) Petite lavande, which jnelds the
finest oil ; (2) Lavande moyenne, which yields' a fine, but less
valued oil ; and (3) Grosse lavaride, which, being a bastard
lavender, yields an inferior oil.

These views have, however, not been entirely accepted by
Humbert, who in 1919—1920 examined the whole of the lavender
position for the French Government, and whose considered views
are the foUowing {vide P. & E. 0. R., 1921, 252). He made very
extensive tours through the principal lavender districts, and his
long investigation and journeys have convinced him that Jordan’s
subdivisions of Lavandula officinalis into two definite varieties is
incorrect. He is quite satisfied that Lavandula officinalis, Chaix,
is a specific entity which, although subject to very great variation,
gives rise in France to only one well-defined geDgraphical race
the Pyrenean {Lavandula pyrenaica, D.C.). On the other hand,
very important and interesting, alike from the industrial and
botanical aspects, is the extreme abundance of hybrids between
lavender and spike {L. latifolia, Vill.), particularly where the areas
of the two plants come into contact. The text-books, where they
do not ignore them altogether, mention these hybrids as excep-
tional, but the result of careful observation carried out during
two summers, when natural lavender fields extending over
hundreds of miles were visited, shows that hybridisation, far from
being rare, takes place in nature with remarkable facfiity.

Spike is a native of relatively low altitudes up to 1,000 metres
when facing south, and no more than 400 metres with a northern
aspect, while lavender commences, broadly speaking, where spike
ceases, and attains to 1,500, or even 1,800 metres above sea-level.

377

PERFU MERY

When cither of the two sj^ccies grows distinct from its all}'-, it
presents a sum of the various distinctive characters (see P. cb
E. 0. R., June, 1921, pp. 177-178) depending on the extension or
compression of the inflorescences, the size of the leaves, etc.,
which makes it quite easy of identification. But it is far otber-
wdse when, ascending from the lower levels to the upper, the
middle region is reached, where the areas of the two come into
contact, or even overlap by encroachment ; here are met, often in
numbers as large as those of the pure si^ecies, plants presenting a
mixture of characters which forces one to assign to them a hybrid
origin. Some of the hybrids are easily distinguished, others less
so (especially' in herbarium specimens) ; these latter have re-
mained until now almost unlcno-wn to botanists, and it is these
which present the greatest danger of mixture with the plants
collected for distillation — for, poor in esters and tainted with
camphor, they lower considerably the linalyl acetate content of
the oil, and destroy its fineness ; in fact, they give an essence
spilce-hke in character.

A consideration of the -wild plants firmly establishes the specific
unity of Lavandula officinalis, and if the hybrids -with spilce are
objectionable from the viewpoint of the quality of the essence, it
does not necessarity follow, either that lavender cannot be divided
into strains or cultural races of diverse characteristics, or that
crossing should, in all cases, be ruled out. On the contrary, it is
probable that a careful selection may enable the separation of
important fines, and that reasoned crossing -with spike may
produce a liigher yield of oil and at the same time maintain a
satisfactory quality.

It has been previously shown (P. dh E. 0. R., 1920, p. 253) that
L. fragrans and L. delpliiniensis, created by Jordan at the expense
of A. officinalis, cannot be considered as distinct species, but merely
as two extreme forms of variationJn accord vdth the local condi-
tions of habitat. Every observation made in the course of last
summer confirms this -view. In all the mountains -visited, -vdthout
exception, from the arid chains of Provence to the high Alpine
valleys, one finds the whole range of variation from one extreme
to the other ; from the short, squat forms -inth compact inflores-
cence,’ subsessile flowers, and linear-revolute leaves {fragrans
corresponding to the most xerophil — i.e., drought-loving —
adaptation : great dryness of air and soil and intense isolation),
to the elongated forms with interrupted and tiered inflorescence,
flowers with distinct pedicels (pedicels sometimes two-fifths of

378

P E E F U M-E R Y

the length of the cah’x), and larger flat leaves {dclphinicnsi-s, the
form of less arid places). NaUirally, the first predominate on the
south and on the dr^' crests of the low mountains, where the battle
against extreme drought induces the morphological modifications
indicated ; the second to the north or in the Jiigh valleys or
higher mountains, where mists and rains are less rare, or again
in the shadow of the forests ; the middle types are found in
situations of an intermediate character ; moreover, these are the
most frequent. Further, one can see one type pass into the other,
following variation in local conditions.

Thus the Luberon shows, on its arid brows (calcareous, of the
lower Cretacean system), towards 1,000 metres high, the most
xerophil forms. But on descending from the summit towards
the north, one meets on the slopes, less exposed to the sun and
principally tow^ards the base, where the soil is no longer purely
calcareous, but a soft Miocene formation and more hygroscopic,
the whole gamut of transitions to, in the neighbourhood of ponds
or rivulets, forms presenting the maximum lengthening of axes
and enlargement of the leaves. The transformation of one form
to the other can be proved experimentally by planting the seed
of the xerophil t3q)e — or even by transplanting a growing plant —
in a damper sofl or climate than the original station, or vice
versd with the other type. As to the first case, which is the more
frequent (cultivation in a valley or plain of plants originally
growing on dry mountains), the morphological modifications are
much accentuated if the plants are put in a rich soil, and still
more so if they are treated with manure. Of the same nature are
the instances where a fall' of rubbish has, by chance, brought
about the layering of some shoots of a xerophil lavender : the
layered branches may show larger leaves and tiered floral glo-
merules. Finally, stocks of the same type after being burnt down,
give forth the following year very vigorous branches, vdth large
leaves and floral glomerules very spaced out by the elongation of
the internodes. The cause of this variation is very simple. The
first shoots which forin after the fire are few in number ; thus they
receive all the sap absorbed by the full uninjured root system,
and at the same time the loss of water by transpiration and
chlorovaporisation is temporarily reduced or suppressed. Hence
everything occurs as if the plant grew in a humid situation — it
loses the characteristics adapted to dryness j the leaves enlarge,
the internodes become elongated. These first 'shoots are very
strong ; the ashes derived from the fire also contribute to their

379

PERFUMERY-

vigour Iby fertilising the soil. During the following years the
shoots multiply, the original conditions tend to return, and the
xerophil characters reappear progressively.

When the original diagnoses of the two Jordanian species are
compared, one is struck by the fact that the characters on which
the author based them distinction are precisely -those which are
easily brought about by change of conditions, and, besides this,
they are merely quantitative characters. Jordan’s own words
relative to L. fmgrans are: Its appearance is very different
(from that of L. clel'phiniensis) ; it forms denser clu

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